Polyolefin resin composition

ABSTRACT

The present invention provides a polyolefin-based resin composition, comprising (A) a polyolefin I produced from at least one monomer selected from the group consisting of α-olefins, cyclic olefins and styrenes; (B) a polyolefin II produced from said at least one monomer, which differs in composition or properties from said polyolefin I; and (C) a graft copolymer produced by bonding said polyolefins I and II to each other through a polyene, wherein (a) a ratio [(1/R 1 )/(1/R 1 ) 0 ] of a relaxation velocity (1/R 1 ) of a long-term relaxation component measured by a solid  1 H-NMR method about the composition to a relaxation velocity (1/R 1 ) 0  of a long-term relaxation component measured by a solid  1 H-NMR method about a resin mixture of only the components (A) and (B) is 1.01 or higher; and (b) an intrinsic viscosity [η] of the composition is in the range of 0.1 to 10 deciliter/g as measured in decalin at 135° C. The resin composition is readily controlled in property-determining factors such as morphology and interfacial strength, and is capable of providing a composite material composed of polyolefin-based resins according to properties as required.

TECHNICAL FIELD

[0001] The present invention relates to a polyolefin-based resincomposition and a molded article produced therefrom. More particularly,the present invention relates to a polyolefin-based resin compositionthat is readily controlled in property-determining factors such asmorphology and interfacial strength and is capable of providing acomposite material composed of polyolefin-based resins which hasproperties as required, by combining optional polyolefin-based resins,especially immiscible resins, and a molded article produced from thecomposition.

BACKGROUND ART

[0002] Conventionally, polyolefin-based resins have been extensivelyused in a variety of applications in the form of various moldedarticles, for example, sheets, films, injection-molded articles,blow-molded articles, foam-molded articles, vacuum-molded articles androtational-molded articles which are formed into desired shapes ordesired properties by various molding methods, because thepolyolefin-based resins are chemically stable, and excellent in weatherresistance, chemical resistance and mechanical strength.

[0003] Also, with a recent increasing tendency toward environmentalprotection, there is such a steady demand that general plastics arerequired to show a less burden to environments. Among them,polyolefin-based resins have been noticed as resins most suitable forreducing the burden to environments because of their excellentrecyclability, good moldability and formation of less harmful componentsupon burning. Therefore, it is expected that the polyolefin-based resinsare more frequently used in future, and are required to show highlyimproved properties.

[0004] However, even if one kind of polyolefin-based material is usedsolely, it is not possible to achieve the highly improved properties orvarious excellent properties as required. Therefore, to meet the aboverequirements, it has been conventionally attempted to combine aplurality of polyolefin-based materials to provide a suitable compositematerial.

[0005] However, in general, since different kinds of polyolefin-basedresins are immiscible with each other, the morphology of the obtainedcomposite material is regulated only to a limited extent, so that such acomposite material fails to exhibit excellent combined properties of therespective polyolefin-based resins as expected.

[0006] On the other hand, Japanese Patent Application Laid-open No. Hei2-281012 discloses a method of polymerizing a vinyl-based monomer or avinylidene-based monomer using a radical polymerization initiator in thepresence of a copolymer of propylene and dialkenyl benzene. Further, inExamples of the above Japanese Patent Application Laid-open No. Hei2-281012, it is described that the thus obtained polymer is used as amiscibilizer for polypropylene and polystyrene.

[0007] In the method described in the above Japanese Patent ApplicationLaid-open No. Hei 2-281012, a radical polymerizable monomer ispolymerized using a radical polymerization initiator to produce graftchains having an atactic structure. Thus, the above method fails toproduce polymers having an isotactic or syndiotactic structure capableof showing a more excellent heat resistance. Further, in the aboveJapanese Patent Application Laid-open No. Hei 2-281012, although it ismerely described that the miscibilizer is applied to a compositematerial composed of isotactic polypropylene and isotactic polystyrene,there is no concrete description concerning application of themiscibilizer to other composite materials.

[0008] In addition, Japanese Patent Application Laid-open No. Hei3-28209 discloses a graft copolymer produced by graft-polymerizingpropylene to an ethylene-α-olefin-diene copolymer and a resincomposition containing the graft copolymer, and further describeseffects obtained by adding the graft copolymer to polypropylene and EPR.However, as shown in Examples of Japanese Patent Application Laid-openNo. Hei 3-28209, since the graft copolymer contains gel componentsinsoluble in a solvent, the obtained composite material is improved inproperties only to a limited extent, and tends to show insufficientsurface properties and poor appearance. Further, since the graftpolymerization is usually conducted using a titanium trichloride typecatalyst, the copolymerizability between diene residues and propylene isextremely low, thereby failing to achieve a high grafting rate.Therefore, since a large amount of graft sites, i.e., carbon-to-carbonunsaturated bonds remain unreacted, the obtained graft copolymer itselfis inevitably deteriorated in heat stability, so that physicalproperties, heat stability, etc., of the composite material producedfrom such a graft copolymer are controlled only to a limited extent.

[0009] Also, the use of the above titanium trichloride type catalystleads to not only production of polypropylene having a broad molecularweight distribution, but also production of a large amount of componentssoluble in ether or the like (low-stereoregular, low-molecular weightcomponents) as well as by-products that do not contribute to improvementin miscibility, thereby causing such a problem that the obtainedcomposite material tends to be deteriorated in physical properties.

DISCLOSURE OF THE INVENTION

[0010] Under the above circumstances, the object of the presentinvention is to provide a polyolefin-based resin composition that isreadily controlled in property-determining factors such as morphologyand interfacial strength and is capable of providing a compositematerial composed of polyolefin-based resins which has properties asrequired, by combining optional polyolefin-based resins, especiallyimmiscible resins.

[0011] As a result of extensive researches for developing thepolyolefin-based resin composition having these excellent properties,the inventors have found that the above object can be achieved by aresin composition that comprises a polyolefin I, a polyolefin II havingdifferent composition and properties from those of the polyolefin I, anda specific graft copolymer, and has specific properties. The presentinvention has been accomplished on the basis of this finding.

[0012] Namely, the present invention provides a polyolefin-based resincomposition, comprising as essential components:

[0013] (A) a polyolefin I produced from at least one monomer selectedfrom the group consisting of C₂ to C₂₀ α-olefins, cyclic olefins andaromatic vinyl compounds;

[0014] (B) a polyolefin II produced from at least one monomer selectedfrom the group consisting of C₂ to C₂₀ α-olefins, cyclic olefins andaromatic vinyl compounds, which differs in at least one of kinds ofconstituting monomer units, stereoregularity, copolymerizationcomposition, copolymerization type and kinds of different bonds, fromthe polyolefin I; and

[0015] (C) a graft copolymer produced by bonding said polyolefins I andII to each other through a polyene, which has a xylene-insoluble contentat 140° C. of 0 to 2.5% by weight, and a polyene-derived residualcarbon-to-carbon double bond content of 0 to 0.15 mol %,

[0016] wherein (a) a ratio [1/R₁)/(1/R₁)₀] of a relaxation velocity(1/R₁) of a long-term relaxation component measured about thecomposition by a solid ¹H-NMR method to a relaxation velocity (1/R₁)₀ ofa long-term relaxation component measured by a solid ¹H-NMR method abouta resin mixture of only the components (A) and (B) is 1.01 or higher;and (b) an intrinsic viscosity [η] of the composition is in the range of0.1 to 10 deciliter/g as measured in decalin at 135° C.

[0017] Also, the present invention provides a molded article producedfrom the above polyolefin-based resin composition.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] The polyolefin-based resin composition of the present inventioncontains as essential components, (A) a polyolefin I, (B) a polyolefinII and (C) a graft copolymer, and may also optionally contain (D) theother thermoplastic resin and/or an additive.

[0019] The polyolefin I as the component (A) is produced from at leastone monomer selected from the group consisting of C₂ to C₂₀ α-olefins,cyclic olefins and aromatic vinyl compounds.

[0020] Examples of the C₂ to C₂₀ α-olefins include α-olefins such asethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene,4-phenyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene,1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicocene and vinyl cyclohexane; and halogen-substitutedα-olefins such as hexafluoropropene, tetrafluoroethylene,2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene,trifluoroethylene and 3,4-dichloro-1-butene.

[0021] Examples of the cyclic olefins include compounds represented bythe general formula (I):

[0022] wherein R¹ to R¹² are independently a hydrogen atom, a C₁ to C₂₀hydrocarbon group, or a substituent group containing halogen, oxygen ornitrogen; m is an integer of 0 or larger; R⁹ or R¹⁰ and R¹¹ or R¹² maybe bonded to each other to form a ring, and R¹ to R¹² may be the same ordifferent.

[0023] In the above general formula (I), examples of the C₁ to C₂₀hydrocarbon group as R¹ to R¹² are C₁ to C₂₀ alkyl groups such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl andhexyl; C₆ to C₂₀ aryl, alkylaryl or arylalkyl groups such as phenyl,tolyl and benzyl; C₁ to C₂₀ alkylidene groups such as methylidene,ethylidene and propylidene; or the like, with the proviso that R¹, R²,R⁵ and R⁶ are not an alkylene group, and if any of R³, R⁴ and R⁷ to R¹²is an alkylidene group, the carbon atom to which the alkylidene group isbonded does not have any substituent group other than the alkylidenegroup.

[0024] Examples of the substituent group containing halogen includehalogen atoms such as fluorine, chlorine, bromine and iodine; C₁ to C₂₀halogen-substituted alkyl groups such as chloromethyl, bromomethyl andchloroethyl; or the like.

[0025] Examples of the substituent group containing oxygen include C₁ toC₂₀ alkoxy or aryloxy groups such as methoxy, ethoxy, propoxy andphenoxy; C₁ to C₂₀ alkoxycarbonyl groups such as methoxycarbonyl andethoxycarbonyl; or the like.

[0026] Examples of the substituent group containing nitrogen include C₁to C₂₀ alkylamino groups such as dimethylamino and diethylamino; cyano;or the like.

[0027] Specific examples of the cyclic olefins represented by the abovegeneral formula (I) include norbornene, 5-methyl norbornene, 5-ethylnorbornene, 5-propyl norbornene, 5,6-dimethyl norbornene, 1-methylnorbornene, 7-methyl norbornene, 5,5,6-trimethyl norbornene, 5-phenylnorbornene, 5-benzyl norbornene, 5-ethylidene norbornene,1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dicyclo-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,2-dihydrodicyclopentadiene, 5-chloronorbornene,5,5-dichloronorbornene, 5-fluoronorbornene,5,5,6-trifluoro-6-trifluoromethyl norbornene, 5-chloromethyl norbornene,5-methoxy norbornene, 5,6-dicarboxyl norbornene anhydrate,5-dimethylaminonorbornene, 5-cyanonorbornene or the like.

[0028] Specific examples of the aromatic vinyl compounds includestyrene; alkyl-styrenes such as p-methyl styrene, p-ethyl styrene,p-propyl styrene, p-isopropyl styrene, p-butyl styrene, p-tert-butylstyrene, p-phenyl styrene, o-methyl styrene, o-ethyl styrene, o-propylstyrene, o-isopropyl styrene, m-methyl styrene, m-ethyl styrene,m-isopropyl styrene, m-butyl styrene, mesityl styrene, 2,4-dimethylstyrene, 2,5-dimethyl styrene and 3,5-dimethyl styrene; alkoxy styrenessuch as p-methoxy styrene, o-methoxy styrene and m-methoxy styrene;halogenated styrenes such as p-chlorostyrene, m-chlorostyrene,o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene,p-fluorostyrene, m-fluorostyrene, o-fluorostyrene ando-methyl-p-fluorostyrene; trimethylsilyl styrene; vinylbenzoic acidesters; or the like.

[0029] Examples of the polyolefin I as the component (A) include (1)ethylene homopolymers or ethylene-based copolymers containing ethyleneunits in an amount of more than 50 mol % which are obtained bycopolymerizing ethylene with at least one compound selected from thegroup consisting of C₃ to C₂₀ α-olefins, cyclic olefins and aromaticvinyl compounds; (2) propylene homopolymers or propylene-basedcopolymers containing propylene units in an amount of more than 50 mol %which are obtained by copolymerizing propylene with at least onecompound selected from the group consisting of C₄ to C₂₀ α-olefins,cyclic olefins and aromatic vinyl compounds, and in which the propylenechains have a stereoregularity of an atactic, syndiotactic (rrrr=35 to100 mol %) or isotactic (mmmm=35 to 100 mol %) structure; (3) C₄ to C₂₀α-olefin homopolymers, α-olefin-based copolymers obtained bycopolymerizing at least two compounds selected from the group consistingof C₄ to C₂₀ α-olefins, or α-olefin-based copolymers containing C₄ toC₂₀ α-olefin units in an amount of more than 50 mol % which are obtainedby copolymerizing at least one compound selected from the groupconsisting of C₄ to C₂₀ α-olefins with at least one compound selectedfrom the group consisting of ethylene, propylene, cyclic olefins andaromatic vinyl compounds; (4) aromatic vinyl compound homopolymers,aromatic vinyl compound-based copolymers obtained by copolymerizing atleast two compounds selected from the group consisting of aromatic vinylcompounds, or aromatic vinyl compound-based copolymers containingaromatic vinyl compound units in an amount of more than 50 mol % whichare obtained by copolymerizing at least one compound selected from thegroup consisting of aromatic vinyl compounds with at least one compoundselected from the group consisting of C₂ to C₂₀ α-olefins and cyclicolefins, and in which the aromatic vinyl compound chains have astereoregularity of an atactic, syndiotactic (rrrr=35 to 100 mol %) orisotactic (mmmm=35 to 100 mol %) structure; (5) cyclic olefinhomopolymers, cyclic olefin-based copolymers obtained by copolymerizingat least two compounds selected from the group consisting of cyclicolefins, or cyclic olefin-based copolymers containing cyclic olefinunits in an amount of more than 50 mol % which are obtained bycopolymerizing at least one compound selected from the group consistingof cyclic olefins with at least one compound selected from the groupconsisting of C₂ to C₂₀ α-olefins and aromatic vinyl compounds; or thelike.

[0030] Specific examples of the above ethylene homopolymers andethylene-based copolymers (1) include HDPE (high-density polyethylene),ethylene/propylene copolymer, ethylene/butene copolymer, ethylene/hexenecopolymer, ethylene/octene copolymer, ethylene/decene copolymer,ethylene/eicosene copolymer, ethylene/styrene copolymer,ethylene/p-methyl styrene copolymer, ethylene/propylene/styrenetercopolymer, ethylene/p-phenyl styrene copolymer, ethylene/norbornenecopolymer or the like.

[0031] Specific examples of the above propylene homopolymers andpropylene-based copolymers (2) include isotactic polypropylene,syndiotactic polypropylene, atactic propylene, low-stereoregularisotactic polypropylene, propylene/ethylene copolymer, propylene/butenecopolymer, propylene/hexene copolymer, propylene/octene copolymer,propylene/decene copolymer, propylene/eicosene copolymer,propylene/norbornene copolymer, propylene/styrene copolymer,propylene/p-methyl styrene copolymer, propylene/ethylene/styrenetercopolymer, propylene/p-phenyl styrene copolymer or the like.

[0032] Specific examples of the above C₄ to C₂₀ α-olefin homopolymersand C₄ to C₂₀ α-olefin-based copolymers (3) include polybutene,butene/ethylene copolymer, butene/propylene copolymer, butene/decenecopolymer, butene/eicosene copolymer, butene/styrene copolymer,butene/ethylene/styrene tercopolymer, butene/norbornene copolymer,poly-4-methyl-penten-1, copolymers obtained by replacing butene of theabove butene-based copolymers with 4-methyl-penten-1, or the like.

[0033] Specific examples of the above aromatic vinyl compoundhomopolymers and aromatic vinyl compound-based copolymers (4) includeisotactic polystyrene, syndiotactic polystyrene, atactic polystyrene,styrene/ethylene copolymer, styrene/propylene copolymer,styrene/ethylene/propylene tercopolymer, styrene/octene copolymer,styrene/decene copolymer, styrene/eicosene copolymer, styrene/norbornenecopolymer, styrene/p-methyl styrene copolymer or the like.

[0034] Specific examples of the above cyclic olefin homopolymers andcyclic olefin-based copolymers (5) include polynorbornene,norbornene/ethylene copolymer, norbornene/propylene copolymer,norbornene/styrene copolymer or the like.

[0035] In the present invention, as the polyolefin I as the component(A), there may be preferably used those polyolefins having the followingproperties.

[0036] First, the intrinsic viscosity [η] of the polyolefin I asmeasured at 135° C. in decalin which is used as an index of a molecularweight thereof is preferably in the range of 0.1 to 10 deciliter/g. Whenthe intrinsic viscosity [η] is less than 1 deciliter/g, the obtainedcomposition tends to be deteriorated in mechanical properties. On theother hand, when the intrinsic viscosity [η] exceeds 10 deciliter/g, theobtained composition tends to be deteriorated in moldability. For thesereasons, the intrinsic viscosity [η] of the polyolefin I is morepreferably 0.15 to 8 deciliter/g, still more preferably 0.20 to 7deciliter/g, further still more preferably 0.50 to 6 deciliter/g andmost preferably 0.70 to 5 deciliter/g.

[0037] Also, although the molecular weight distribution of thepolyolefin I is not particularly restricted, the ratio (Mw/Mn) ofweight-average molecular weight (Mw) to number-average molecular weight(Mn) thereof as measured by gel permeation chromatography (GPC) isusually in the range of 1.5 to 60.

[0038] As previously described, the steric configuration(stereoregularity) of the polyolefin I may be an isotactic, syndiotacticor atactic structure. As to the range of the stereoregularity, theisotactic structure preferably has a pentad fraction [mmmm] of 35 to 100mol %, and the syndiotactic structure preferably has a pentad fraction[rrrr] of 35 to 100 mol %.

[0039] Here, [mmmm] means a proportion of such a steric structure inwhich all of five side chain groups are present on the same siderelative to the carbon-to-carbon bond main chain constituted by optionalcontinuous five monomers, and [rrrr] means a proportion of such a stericstructure in which five side chain groups are alternately present on theopposite sides relative to the carbon-to-carbon bond main chainconstituted by optional continuous five monomers.

[0040] Further, as to the copolymerization type of the polyolefin I, itmay be in the form of any of a random copolymer, a block copolymer, agraft copolymer and an alternating copolymer.

[0041] On the other hand, the polyolefin II as the component (B) isproduced from at least one monomer selected from the group consisting ofC₂ to C₂₀ α-olefins, cyclic olefins and aromatic vinyl compounds. Themonomers used for production of the polyolefin II are the same as thosedescribed above for the polyolefin I.

[0042] Specific examples of the polyolefin II include the same compoundsas specified above for the polyolefin I. As the polyolefin II as thecomponent (B), there may be used such polyolefins that are different inat least one of kinds of constituting monomer units, stereoregularity,copolymerization composition, copolymerization type and kinds ofdifferent bonds, from those of the polyolefin I.

[0043] Here, the condition that the polyolefins I and II are differentin kinds of constituting monomer units from each other, means that thepolyolefins I and II is different in at least one kind of constitutingmonomer unit from each other, or that one of the polyolefins I and IIcontains such a monomer unit that is not contained in the other of thepolyolefins I and II. For example, this condition indicates therelationships between polyethylene and polypropylene, betweenethylenefbutene copolymer and polyethylene, between ethylene/butenecopolymer and ethylene/octene copolymer, between propylenefbutenecopolymer and propylene/butene/octene tercopolymer, or the like.

[0044] Also, the condition that the polyolefins I and II are differentin stereoregularity from each other, means that the polyolefins I and IIthat are identical in constituting monomer units and are in the form ofeither homopolymers produced from the same monomer selected from thegroup consisting of C₃ to C₂₀ α-olefins, cyclic olefins and aromaticvinyl compounds, or copolymers produced from the same two or moremonomers selected from the group consisting of C₂ to C₂₀ α-olefins,cyclic olefins and aromatic vinyl compounds, are different instereoregularity (i.e., three steric configurations including isotactic,syndiotactic and atactic structures) from each other. For example, thecombination of the polyolefins I and II that are different instereoregularity may be any of three combinations includingatactic/isotactic, atactic/syndiotactic and isotactic/syndiotactic. Thecondition that the polyolefins I and II are different instereoregularity from each other also involves such a condition thateven though the polyolefins I and II are identical in kind ofstereoregularity to each other, for example, are composed of any ofcombinations of isotactic/isotactic and syndiotactic/syndiotactic, bothare different in stereoregular range, i.e., different in pentad fraction(mmmm=35 to 100 mol % or rrrr=35 to 100 mol %) from each other, forexample, in such a combination in which a ratio between the pentadfractions (mmmm or rrrr) of the polyolefins I and II is in the range of1.3 to 2.85.

[0045] Specific examples of the combinations of the polyolefins I and IIthat are different in stereoregularity from each other include isotacticpolypropylene and syndiotactic polypropylene; atactic polypropylene andisotactic polypropylene; atactic polypropylene and syndiotacticpolypropylene; isotactic polystyrene and syndiotactic polystyrene;atactic polystyrene and isotactic polystyrene; atactic polystyrene andsyndiotactic polystyrene; low-stereoregular isotactic polypropylene andhigh-stereoregular isotactic polypropylene; or the like.

[0046] The condition that the polyolefins I and II are different incopolymerization composition from each other, means that the polyolefinsI and II are identical in constituting monomer units, but are notidentical in composition of copolymers involved. In this case, assumingthat the monomer units constituting the copolymer are represented by a₁,a₂, a₃, a₄ . . . a_(n), and the contents of the respective monomer unitsof the polyolefin I are C^(I)(a_(n)) [n=1, 2, 3, 4 . . . n; unit: mol %]and the contents of the respective monomer units of the polyolefin IIare C^(II)(a_(n)) [n=1, 2, 3, 4 . . . n; unit: mol %], the preferredcombinations of the polyolefins I and II are those in which the ratio ofC^(I)(a_(n))/C^(II)(a_(n)) or C^(II)(a_(n))/C^(I)(a_(n)) is preferably1.2 or higher, more preferably 1.5 or higher, still more preferably 2.0or higher, further still more preferably 2.5 or higher and mostpreferably 3.0 or higher.

[0047] When the above ratio is less than 1.2, the polyolefins I and IIare analogous in mechanical properties or thermal properties, so thatthe composite polyolefin-based material obtained by combining thesepolyolefins may fail to show improved properties as aimed by the presentinvention. The upper limit of the above ratio is not particularlyrestricted since the larger ratio indicates the larger differencebetween properties of the polyolefins I and II, so that the compositionhaving the aimed properties can be obtained by combining thesepolyolefins.

[0048] The condition that the polyolefins I and II are different incopolymerization type from each other, means that the polyolefins I andII are composed of combinations of any different two copolymers selectedfrom random copolymer, block copolymer, alternating copolymer and graftcopolymer as generally defined. The block copolymer includes, inaddition to ordinary block copolymers constituted from mutually bondedblocks each composed of monomer units with an optional length,polypropylene-based resins produced by multi-stage polymerizationreaction, i.e., so-called block polypropylenes as well as stereoregularblock copolymers showing such a stereoregularity which varies at everyoptional chain length in the molecular chain, etc.

[0049] The condition that the polyolefins I and II are different inkinds of different bonds from each other, means that the bonds containedin the polyolefins I and II are different in kind from each other. Thedifferent kinds of bonds include head-to-head bond and tail-to-tail bondas well as 1,3-bond in α-olefins such as propylene or styrene-basedmonomers.

[0050] In the present invention, as the polyolefin II as the component(B), there may be preferably used those polyolefins having the followingproperties.

[0051] First, the polyolefin II preferably has an intrinsic viscosity[η] of 0.1 to 10 deciliter/g as measured at 135° C. in decalin. When theintrinsic viscosity [η] of the polyolefin II is less than 0.1deciliter/g, the obtained composition tends to be deteriorated inmechanical properties. When the intrinsic viscosity [η] exceeds 10deciliter/g, the composition tends to be deteriorated in moldability.For these reasons, the intrinsic viscosity [η] of the polyolefin II ismore preferably 0.15 to 8 deciliter/g, still more preferably 0.20 to 7deciliter/g, further still more preferably 0.50 to 6 deciliter/g andmost preferably 0.70 to 5 deciliter/g.

[0052] The molecular weight distribution of the polyolefin II is notparticularly restricted, but is usually in such a range that the ratio(Mw/Mn) of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn) thereof as measured by GPC methodis 1.5 to 60.

[0053] The graft copolymer used as the component (C) in the compositionof the present invention includes those polymers obtained by bonding theabove polyolefins I and II to each other through a polyene. That is, thegraft copolymer contains in the same molecule, two differentpolyolefin-based polymers as segments which are selected from thoseillustrated above for the polyolefin I but are different in at least oneof constituting monomer units, stereoregularity, copolymerizationcomposition, copolymerization type and kinds of different bonds, fromeach other, and which are bonded to each other through a polyene,

[0054] Specific examples of combinations of the two segmentsconstituting the graft copolymer include: Segment 1 Segment 2Combinations that are different in stereoregularity: Isotacticpolypropylene Atactic polypropylene Isotactic polypropylene Syndiotacticpolypropylene Atactic polypropylene Syndiotactic polypropylene Isotacticpolystyrene Atactic polystyrene Isotactic polystyrene Syndiotacticpolystyrene Atactic polystyrene Syndiotactic polystyrene;

[0055] Combinations that are different in kinds of monomer units:Isotactic polypropylene Ethylene/α-olefin copolymer (propylene, butene,etc.) Isotactic polypropylene Polyethylene Syndiotactic polypropylenePolyethylene Syndiotactic polystyrene Polyethylene Isotacticpolypropylene Ethylene/norbornene copolymer Isotactic polypropyleneEthylene/propylene/styrene copolymer Polyethylene Ethylene/norbornenecopolymer Syndiotactic polystyrene Polyethylene Syndiotactic polystyreneEthylene/α-olefin copolymer (propylene, butene, etc.) Syndiotacticpolystyrene Ethylene/propylene/styrene copolymer Atactic polystyreneEthylene/propylene/styrene copolymer Polyethylene PolybutenePolyethylene Ethylene/propylene copolymer PolyethyleneEthylene/propylene/styrene copolymer Polypropylene Polybutene;

[0056] Combinations that are different in stereoregularity and kinds ofmonomer units: Isotactic polypropylene Syndiotactic polystyreneIsotactic polypropylene Isotactic polystyrene Syndiotactic polypropyleneIsotactic polystyrene Atactic polystyrene Syndiotactic polypropylene;

[0057] Combinations that are different in copolymerization composition:Ethylene/propylene copolymer Ethylene/propylene copolymerPropylene/butene coolymer Propylene/butene copolymer

[0058] Among these combinations, those having copolymerizationcompositions within the range as defined herein;

[0059] Combinations that are different in copolymerization type:Ethylene/propylene random Ethylene/propylene block copolymer copolymerEthylene/styrene Ethylene/propylene block copolymer pseudo-randomcopolymer Long-chain branched ethylene/ Ethylene/propylene randomcopolymer propylene copolymer or the like.

[0060] The polyene used in the graft copolymer is not particularlyrestricted, and may include various compounds having at least twopolymerizable carbon-to-carbon double bonds in one molecule. As thepreferred polyene, there may be used, for example, the followingcompounds (a) to (e):

[0061] (a) α, ω-type polyenes:

[0062] Compounds represented by the general formula (II):

CH₂═CH—Q—CH═CH₂  (II)

[0063] wherein Q is a single bond or C₀ to C₂₀ alkylene.

[0064] Examples of the α, ω-type polyenes include 1,3-butadiene,1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene,1,13-tetradecadiene, 1,15-hexadecadiene, 4-methyl-1,9-decadiene,4,4-dimethyl-1,9-decadiene, 5-allyl-1,9-decadiene, 1,19-eicodiene or thelike.

[0065] (b) Styrene-type polyenes:

[0066] Compounds represented by the general formula (III):

[0067] wherein R¹³ is a hydrogen atom, a halogen atom or a substituentgroup containing carbon and/or silicon; R¹⁴ is a substituent groupcontaining an α-olefin residue; and a is an integer of 1 to 4 with theproviso that when a is 2 or larger, the plural R¹³ groups may be thesame or different.

[0068] Examples of the styrene-type polyenes include p-divinylbenzene,m-divinylbenzene, o-divinylbenzene, di(p-vinylphenyl)methane,1,3-bis(p-vinylphenyl)propane, 1,5-bis(p-vinylphenyl)pentane or thelike.

[0069] (c) Cyclic polyenes:

[0070] Compounds having an unsaturated bond and a norbornene skeletonrepresented by the general formula (IV):

[0071] wherein R¹⁵ to R²⁴ are independently a hydrogen atom, a halogenatom or a C₁ to C₂₀ hydrocarbon group with the proviso that R¹⁵ to R²⁴may be the same or different; R is C₂ to C₂₀ alkenyl; and n is aninteger of 0 or larger, or

[0072] Compounds having a cyclopentene skeleton and a norborneneskeleton represented by the general formula (V):

[0073] wherein R¹⁵ to R²⁴ and n are the same as defined above.

[0074] Examples of the halogen atom as R¹⁵ to R²⁴ include chlorine,fluorine, bromine, etc. Examples of the C₁ to C₂₀ hydrocarbon group asR¹⁵ to R²⁴ include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclohexyl, octyl, decyl, dodecyl, tetradecyl, pentadecyl, heptadecyl,octadecyl, etc., as well as corresponding alkoxy groups thereof. The R¹⁵to R²⁴ groups may be the same or different.

[0075] Specific examples of the compounds represented by the abovegeneral formula (IV) include 5-vinyl-2-norbornene,5-(3-butenyl)-2-norbornene, 5-allyl-2-norbornene,5-(4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene or the like.Specific examples of the compounds represented by the above generalformula (V) include cyclopentadiene, dimethyl dicyclopentadiene, diethyldicyclopentadiene or the like.

[0076] Also, as the cyclic polyenes (c), there may be used compoundsrepresented by the general formula (VI):

[0077] wherein b is 0, 1 or 2.

[0078] Examples of the compounds represented by the general formula (VI)include bicyclo[2.2.1.]hepto-2,5-diene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3,8-dodecadiene,hexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]-4,11-heptadecadieneor the like.

[0079] In addition, as the cyclic polyenes (c), there may also be usedcompounds represented by the general formula (VII):

[0080] wherein c is an integer of 1 or 2; and d is an integer of 0 to11, and compounds represented by the general formula (VIII):

[0081] wherein e is an integer of 0 to 6.

[0082] Examples of the compounds represented by the general formula(VII) include 5-vinyl bicyclo[2.2.1]hepto-2-ene, 5-allylbicyclo[2.2.1]hepto-2-ene, 5-(3-butenyl)bicyclo[2.2.1]hepto-2-ene,8-vinyl tetracyclo[4.4.0.1^(2,5).1^(7,10)]-3-dodecene, 11-vinylhexacyclo[6.6.1.1^(3,6).1^(10,13).0^(2,7).0^(9,14)]-4-heptadecene or thelike. Examples of the compounds represented by the general formula(VIII) include 1,1-bis(5-bicyclo[2.2.1]hept-2-enyl)methane,1,2-bis(5-bicyclo[2.2.1]hept-2-enyl) ethane,1,6-bis(5-bicyclo[2.2.1]hept-2-enyl)hexane or the like.

[0083] (d) Styrene/α-olefin-type polyenes:

[0084] Compounds represented by the general formula (IX):

[0085] wherein R²⁵ is a divalent C₁ to C₂₀ hydrocarbon group; R²⁶ is ahalogen atom or a C₁ to C₈ hydrocarbon group; R²⁷ and R²⁸ areindependently a hydrogen atom, a halogen atom or a C₁ to C₈ hydrocarbongroup; and f is an integer of 0 to 4.

[0086] Examples of the divalent C₁ to C₂₀ hydrocarbon group as R²⁵ inthe general formula (IX) include C₁ to C₂₀ alkylene, C₆ to C₂₀ arylene,C₇ to C₂₀ alkylarylene, C₇ to C₂₀ arylalkylene or the like. Specificexamples of the divalent C₁ to C₂₀ hydrocarbon group as R²⁵ includemethylene, ethylene, propylene, butylene, pentylene, hexylene,phenylene, tolylene or the like. Examples of the halogen atom as R²⁶include chlorine, bromine, fluorine and iodine. Examples of the C₁ to C₈hydrocarbon group as R²⁶ include saturated hydrocarbon groups,typically, for example, alkyl groups such as methyl, ethyl, propyl,butyl and pentyl, unsaturated hydrocarbon groups such as vinyl, or thelike. Examples of the halogen atom and the C₁ to C₈ hydrocarbon group asR²⁷ and R²⁸ are the same as described above. Specific examples of thecompounds represented by the general formula (IX) in which R25 isalkylene, include p-(2-propenyl)styrene, m-(2-propenyl)styrene,p-(3-butenyl)styrene, m-(3-butenyl)styrene, o-(3-butenyl)styrene,p-(4-pentenyl)styrene, m-(4-pentenyl)styrene, o-(4-pentenyl)styrene,p-(7-octenyl)styrene, p-(1-methyl-3-butenyl)styrene,p-(2-methyl-3-butenyl)styrene, m-(2-methyl-3-butenyl)styrene,o-(2-methyl-3-butenyl)styrene, p-(3-methyl-3-butenyl)styrene,p-(2-ethyl-3-butenyl)styrene, p-(2-ethyl-4-pentenyl)styrene,p-(3-butenyl)-α-methyl styrene, m-(3-butenyl)-α-methyl styrene,o-(3-butenyl)-α-(x-methyl styrene or the like.

[0087] Also, specific examples of the compounds represented by thegeneral formula (IX) in which R²⁵ is arylene, include4-vinyl-4′-(3-butenyl)biphenyl, 4-vinyl-3′-(3-butenyl)biphenyl,4-vinyl-4′-(4-pentenyl)biphenyl, 4-vinyl-2′-(4-pentenyl)biphenyl,4-vinyl-4′-(2-methyl-3-butenyl)biphenyl or the like.

[0088] (e) Other polyenes:

[0089] Further, as the polyene, there may be used monoalicyclic dienecompounds. Specific examples of the monoalicyclic diene compoundsinclude 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5-cyclododecadiene,4-vinyl cyclohexane, 1-allyl-4-isopropylidene cyclohexane, 3-allylcyclopentene, 4-allyl cyclohexene,1-isopropenyl-4-(4-butenyl)cyclohexane or the like.

[0090] Among these polyenes, preferred are those polyenes having ahigh-polymerizable carbon-to-carbon bonds and containing a less amountof residual unsaturated bonds that tend to cause deterioration inthermal stability upon production of the composition. Such preferredpolyenes are the α-,ω-type polyenes (a), the styrene-type polyenes (b),the compounds (c) represented by the general formulae (VI), (VII) and(VIII), and the styrene/α-olefin-type polyenes (d).

[0091] In the present invention, the graft copolymer as the component(C) is required to have a 140° C. xylene insoluble content of 0 to 2.5%by weight. When the 140° C. xylene insoluble content exceeds 2.5% byweight, the graft copolymer is insufficiently dispersed and mixed in amelt or solution upon production of the resin composition, therebyfailing to obtain the composition having the aimed properties, andfurther a molded article produced therefrom tends to show a poorappearance and suffer from deterioration in breaking strength due toconcentrated stress. Therefore, the 140° C. xylene insoluble content ofthe graft copolymer (C) is preferably 0 to 1.5% by weight, morepreferably 0 to 1.2% by weight, still more preferably 0 to 1.0% byweight, further still more preferably 0 to 0.5% by weight and mostpreferably 0 to 0.3% by weight.

[0092] The above xylene insoluble content is measured by the followingmethod. That is, 2.0 g of the graft copolymer is placed in a 150 meshstainless steel container, immersed in one liter of p-xylene at 140° C.and dissolved therein while stirring for 5 hours. After completion ofthe dissolution, the container is removed from the p-xylene bath, andthe residual graft copolymer in the container is dried at 100° C. underreduced pressure until reaching a constant weight. The weight of thegraft copolymer remaining in the container is divided by the weight ofthe graft copolymer initially charged to determine the p-xyleneinsoluble content (%) in the graft copolymer.

[0093] The graft copolymer as the component (C) may be generallyproduced by the following method, i.e., the method comprising the step[step 1] of producing an polyolefin containing a polyene residue, andthe step [step 2] of subjecting the polyolefin obtained in the step 1 tograft copolymerization. In this case, in order to control and reduce thep-xylene insoluble content in the resultant graft copolymer, thefollowing methods can be adopted.

[0094] Method (i): After completion of the step 1, the reaction solutionis subjected to washing, etc., to remove unreacted polyene therefrom,followed by conducting the step 2.

[0095] In the method (i), it is preferred to use a slurry polymerizationprocess for the step 1, and use a washing solvent incapable ofdissolving the obtained polyolefin containing a polyene residue, sincethe polyolefin resin composition of the present invention can beproduced with a high efficiency.

[0096] Method (ii): Two kinds of polyenes that are different inpolymerizable sites from each other are employed in the steps 1 and 2,respectively.

[0097] Method (iii): Two kinds of metallocene catalysts that aredifferent in polymerizable sites from each other are employed in thesteps 1 and 2, respectively.

[0098] In particular, the combination of the methods (i), (ii) and (iii)is preferred.

[0099] In the present invention, the graft copolymer as the component(C) contains a polyene unit as an essential unit. The polyene unitcontent [D] in the graft copolymer is as small as usually 0.45 mol % orlower, preferably 0.40 mol % or lower, more preferably 0.35 mol % orlower, still more preferably 0.30 mol % or lower, further still morepreferably 0.25 mol % or lower and most preferably 0.20 mol % or lower.When the polyene unit content [D] exceeds 0.45 mol %, there tends toarise the same problem as in the case where the xylene insoluble contentexceeds 2.5% by weight.

[0100] The polyene unit content [D] may be measured by the followingmethod.

[0101] Since one of features of the present invention resides in thatthe graft copolymer contains a small polyene unit content, it isrequired to select a measuring method suitable for detecting even atrace amount of the polyene unit.

[0102] (1) NMR method is used to quantitatively determine the polyeneunit content when the content is close to its upper limit irrespectiveof the structure of the polyene component. The range measurable by thismethod is approximately from 0.05 to 0.45 mol % as the upper limitvalue.

[0103] (2) Infrared absorption spectrum method or ultraviolet absorptionspectrum method is employable in the case where the polyene unit contentis still smaller. However, in any of these methods, it is required thatthe polyene unit structure introduced into the graft copolymer has aspecific absorption band in these spectra. In these methods, thedetection limit is improved about 10 to 50 times that of the method (1).

[0104] (3) As the useful method for measuring a minute polyene unitcontent in the graft copolymer, there may also be used a method ofevaluating a kinematic viscoelasticity of the graft copolymer from anangular velocity dependence thereof. The measuring method is based onsuch a fact that the shear rate-dependence of melt viscosity of apolyolefin containing a branched structure due to the polyene unit evenin a minute amount is different from that of a polyolefin containing nobranched structure.

[0105] Namely, the shear rate dependency of melt viscosity of thepolyolefin having such a branched structure due to the polyene unit islarger than that of the polyolefin containing no branched structure.Therefore, the polyene unit forming the branched structure can bedetected by comparing the shear rate dependency of melt viscosity of thegraft copolymer with that of the polymer produced under the sameconditions as those of the graft copolymer except for using no polyene.

[0106] Further, it is known that the above method is adversely affectedby the molecular weight distribution of the polymer to be measured.However, in this case, by comparing the shear rate dependency of meltviscosity of the graft copolymer relative to its molecular weightdistribution with that of the polyolefin apparently having no branchedstructure and containing the same kind of constituting monomer unit atthe substantially same content, the polyene unit forming the branchedstructure can be surely detected.

[0107] The specific measuring method is exemplified below.

[0108] Apparatus: Melt viscosity-measuring device “RMS800” produced byRheometrics Inc.

[0109] Measuring Conditions:

[0110] Temperature: Melting point or glass transition temperature orhigher of the graft copolymer;

[0111] Usually, there is used a temperature higher by 10 to 60° C. thanthe maximum melting point of the graft copolymer, or a temperaturehigher by 10 to 200° C. than the maximum glass transition temperature ofthe graft copolymer.

[0112] Deflection: 15%;

[0113] Angular velocity: 0.01 to 100 rad/sec.;

[0114] Shape of specimen: Cone plate shape;

[0115] Data processing:

[0116] The value of ω2/10ω1 wherein ω1 represents an angular velocity ata storage elastic modulus of 10 Pa and ω2 represents an angular velocityat a storage elastic modulus of 10³ Pa is calculated.

[0117] <Detection of Polyene Unit>

[0118] Case 1:

[0119] In the case of using as a comparative specimen, a polyolefinwhich is produced under the same conditions as those of the graftcopolymer except for using no polyene, and has a molecular weightdistribution [weight-average molecular weight (Mw)/number-averagemolecular weight (Mn)] of 0.8 to 1.8 times that of the graft copolymer:

[0120] When the following formula (a) wherein N¹ represents the value ofω2/10ω1 of the graft copolymer and N⁰ represents the value of ω02/10ω1of the comparative specimen is satisfied, it is determined that thepolyene unit is present in the graft copolymer.

[0121] Case 2:

[0122] In the case where the comparative specimen is made of apolyolefin apparently containing no branched structure and having thesame kind and content of constituting monomer units as those of thegraft copolymer, the polyene unit content in the graft copolymer isdetermined by the following method.

[0123] Here, the “same content of constituting monomer units” means thatthe comparative specimen is made of either one of the followingmaterials:

[0124] (1) Polyolefin having the same sequences as those of the graftcopolymer except for sequences derived from the polyene unit; and apolymeric structure other than a grafting structure whose monomercomposition is substantially the same as that of the graft copolymer;and

[0125] (2) Polyolefin mixture containing the polyolefin having the samesequences as those of the graft copolymer except for sequences derivedfrom the polyene unit, and the other polyolefin having a polymericstructure other than a grafting structure, whose monomer composition issubstantially the same as that of the graft copolymer.

[0126] A plurality of comparative specimens (used in the case 2) havingdifferent molecular weight distributions from each other are subjectedto GPC to measure molecular weight distributions [weight-averagemolecular weight (Mw)/number-average molecular weight (Mn)] thereof, andfurther measure values N⁰ (ω2/10ω1) thereof by the above-describedmethod. Then, the thus obtained values of Mw/Mn and N⁰ are plotted todetermine a monotone increasing function N⁰=f(Mw/Mn) by a method ofleast square.

[0127] Next, the molecular weight distribution (Mw/Mn) and N¹ of thegraft copolymer are measured, and the values N⁰ and N¹ are compared witheach other under the same molecular weight distribution. The existenceof the polyene unit in the graft copolymer can be confirmed when theratio of N¹/N⁰ satisfies the following formula (a):

[0128] When the ratio N¹/N⁰ is less than 1.05, the graft copolymer tendsto be deteriorated in miscibility, thereby failing to obtain a compositematerial exhibiting sufficient physical properties. On the other hand,when the ratio N¹/N⁰ exceeds 80, graft copolymers having a cross-linkedstructure are by-produced, resulting in formation of gels and,therefore, poor mixing property upon production of the compositematerial.

[0129] The graft copolymer as the component (C) is required to containresidual carbon-to-carbon double bonds derived from the polyene unit inan amount of 0 to 0.15 mol %. Meanwhile, the residual unsaturated bondsdefined herein mean those derived from the polyene unit, but do notinvolve carbon-to-carbon double bonds bonded to terminals of polymersnewly produced during the production process. When the amount of theresidual carbon-to-carbon double bonds exceeds 0.15 mol %, the obtainedcomposition tends to be deteriorated in weather resistance and thermalstability. The amount of the residual carbon-to-carbon double bondscontained in the graft copolymer is preferably 0 to 0.13 mol %, morepreferably 0 to 0.11 mol %, still more preferably 0 to 0.09 mol %,further still more preferably 0 to 0.07 mol % and most preferably 0 to0.05 mol %.

[0130] Also, the amount of the residual carbon-to-carbon double bonds isusually 0 to 30 mol %, preferably 0 to 28 mol %, more preferably 0 to 25mol %, still more preferably 0 to 22 mol %, further still morepreferably 0 to 18 mol % and most preferably 0 to 15 mol % based on thepolyene unit.

[0131] The amount of the residual carbon-to-carbon double bonds derivedfrom the polyene unit can be measured according to ordinary methods suchas infrared absorption spectrum method and ultraviolet absorptionspectrum method. Since the graft copolymer inherently contains a verysmall amount of the polyene unit, the amount of the unreactedcarbon-to-carbon double bonds is further reduced. Therefore, if theamount of the residual carbon-to-carbon double bonds is below thedetection limits of the above measuring methods and is thereforeunmeasurable, the graft copolymer is regarded to contain substantiallyno unreacted carbon-to-carbon double bonds therein.

[0132] The graft copolymer as the component (C) may be generallyproduced by the following method, i.e., the method comprising the step[step 1] of producing a polyolefin containing a polyene residue, and thestep [step 2] of subjecting the polyolefin obtained in the step 1 tograft copolymerization. In this case, in order to control and reduce theamount of the residual carbon-to-carbon double bonds contained in theresultant graft copolymer, the following methods can be adopted.

[0133] Method (i): The probability of reaction between the polyolefincontaining a polyene residue and the monomer in the step 2 is increased.For this purpose, the polymerization time of the step 2 is prolonged, orthe step 2 is conducted in the presence of a carrier-supported catalyst.

[0134] Method (ii): The step 2 is conducted in the presence of acatalyst showing a high copolymerization reactivity between the polyeneresidue and the monomer. As such a catalyst, there may be used catalystsemployed in the below-mentioned Production Examples.

[0135] The graft copolymer as the component (C) is a graft copolymercontaining segments having substantially the same chain structures asthose of the polyolefin I as the component (A) and the polyolefin II asthe component (B), respectively, which are bonded to each other througha polyene, in the same molecule. The graft copolymer (C) is notparticularly limited in its structure as long as it exhibits a xyleneinsoluble content and an amount of unreacted carbon-to-carbonunsaturated bonds as defined in the present invention, and satisfies thecondition that a relaxation velocity ratio of the resultant compositionas measured by solid ¹H-NMR method lies in the range as defined in thepresent invention. Preferably, the graft copolymer has the followingintrinsic viscosity, stereoregularity and copolymerization composition.

[0136] (1) Intrinsic Viscosity:

[0137] The intrinsic viscosity [η] of the graft copolymer (C) asmeasured at 135° C. in decalin is preferably 0.1 to 10 deciliter/g, morepreferably 0.2 to 9 deciliter/g, still more preferably 0.3 to 8deciliter/g and most preferably 0.4 to 7 deciliter/g. When the intrinsicviscosity [η] is less than 0.1 deciliter/g, it may be difficult to wellcontrol properties of the obtained composition. When the intrinsicviscosity [η] exceeds 10 deciliter/g, the graft copolymer tends to bedeteriorated in dispersibility upon production of the composition.

[0138] (2) Stereoregularity:

[0139] The ratio of (mmmm)g/(mmmm)po or the ratio of (rrrr)g/(rrrr)po ispreferably 0.5 to 1.5, more preferably 0.6 to 1.4, still more preferably0.65 to 1.35, further still more preferably 0.67 to 1.30 and mostpreferably 0.70 to 1.25. Meanwhile, the (mmmm)g or (rrrr)g representsthe stereoregularity of the graft copolymer, and the (mmmm)po or(rrrr)po represents the stereoregularity of a portion of the polyolefinI or polyolefin II corresponding to the respective segments of the graftcopolymer. When the ratio is less than 0.5 or exceeds 1.5, the graftcopolymer tends to be deteriorated in miscibility with the polyolefin Ior polyolefin II, thereby failing to improve properties of the obtainedcomposition.

[0140] (3) Copolymerization Composition:

[0141] The compositions of respective monomer units present in thepolyolefin I or II are represented by a_(po), b_(po), c_(po) . . . ,n_(po).

[0142] On the other hand, the compositions of respective monomer unitspresent in the segments of the graft copolymer corresponding topolyolefin I or II are represented by a_(g), b_(g), c_(g) . . . , n_(g).

[0143] Here, a, b, c . . . , n represent compositions of the respectivemonomer units, and a+b+c+ . . . +n=100%

[0144] The maximum value of the ratio of n_(po)/n_(g) or n_(g)/n_(po)(either one is selected so as to be 1 or higher; n represents a, b, c .. . , n) is preferably 20 or smaller, and the minimum value of the ratiois preferably 1.5 or smaller. When the ratio is out of theabove-specified range, the obtained composite material tends to beinsufficient in physical properties thereof. On the other hand, when theratio is within the above range, there occurs no problem even though asmall amount of the third monomer unit is contained in the graftcopolymer. The content of the third monomer unit in the graft copolymeris usually 3 mol % or smaller.

[0145] The greater value of the ratio of n_(po)/n_(g) or n_(g)/n_(po) ismore preferably 15 or smaller, still more preferably 10 or smaller,further still more preferably 8 or smaller and most preferably 5 orsmaller, and the little value of the ratio of n_(po)/n_(g) orn_(g)/n_(po) is more preferably 1.4 or smaller, still more preferably1.3 or smaller, further still more preferably 1.25 or smaller and mostpreferably 1.20 or smaller.

[0146] The graft copolymer as the component (C) may be produced, forexample, by slurry polymerization, solution polymerization, gas phasepolymerization, bulk polymerization, etc., using a metallocene-basedcatalyst as a main catalyst together with a co-catalyst composed ofchain or cyclic aluminoxane, an ionic compound such astetrakis(pentafluorophenyl)boric acid N,N-dimethyl anilinium, or a Lewisacid such as triphenyl boric acid. This production method generallycomprises the step [step 1] of producing a polyolefin containing apolyene residue, and the step [step 2] of subjecting the polyolefinobtained in the step 1 to graft copolymerization.

[0147] The polyolefin-based resin composition of the present inventionmay contain, in addition to the polyolefin I as the component (A), thepolyolefin II as the component (B) and the graft copolymer as thecomponent (C), the other thermoplastic resin as the component (D) and/oran additive, if desired. The suitable combination of the components ofthe polyolefin-based resin composition according to the presentinvention include polyolefin I/polyolefin II/graft copolymer, polyolefinI/polyolefin II/graft copolymer/thermoplastic resin, polyolefinI/polyolefin II/graft copolymer/additive, and polyolefin I/pblyolefinII/graft copolymer/thermoplastic resin/additive.

[0148] In the composition of the present invention, the polyolefin I asthe component (A) and the polyolefin II as the component (B) arepreferably used in a weight ratio of 1:99 to 99:1. The graft copolymeras the component (C) is preferably used in an amount of 0.01 to 30% byweight, more preferably 0.05 to 28% by weight, still more preferably0.10 to 26% by weight, further still more preferably 0.20 to 24% byweight and most preferably 0.50 to 22% by weight based on the totalweight of the components (A) and (B). When the amount of the component(C) used is less than 0.01% by weight or exceeds 30% by weight, theobtained composition tends to fail to exhibit aimed properties.

[0149] Also, the other thermoplastic resin as the component (D) is addedin an amount of usually 0.5 to 60% by weight based on the total weightof the components (A), (B) and (C), and the additive is added in anamount of usually 0.0001 to 60% by weight based on the total weight ofthe components (A), (B) and (C).

[0150] The polyolefin-based resin composition of the present inventionhas a relaxation velocity (1/R₁) of its long-term relaxation componentof preferably 0.2 to 10 (1/sec), more preferably 0.3 to 9 (1/sec) andstill more preferably 0.35 to 5 (1/sec) as measured by solid ¹H-NMRmethod. In addition, the composition of the present invention isrequired to satisfy the condition that a ratio [(1/R₁)/(1/R₁)₀] of therelaxation velocity (1/R₁) of the long-term relaxation componentmeasured by solid ¹H-NMR method about the composition to a relaxationvelocity (1/R₁)₀ of a long-term relaxation component measured by solid¹H-NMR method about a resin mixture composed of only the components (A)and (B) is 1.01 or higher. When the ratio [(1/R₁)/(1/R₁)₀] is less than1.01, the resins tends to be deteriorated in miscibility with eachother, thereby failing to obtain the composition having the aimedproperties. The ratio [(1/R₁)/(1/R₁)₀] is preferably 1.02 or higher andmore preferably 1.03 or higher.

[0151] Meanwhile, the ratio [1/R₁)₀] is measured by an invertedrestoration method (180°-τ-90° pulse method) using the following solid¹H-NMR measuring device.

[0152] Apparatus: “CPX-902” produced by Bluker Inc.

[0153] Nucleus to be measured: Hydrogen nucleus (1H)

[0154] Measuring frequency: 90 MHz

[0155] Measuring temperature: The relaxation velocities of the long-termrelaxation components of the polyolefins I and II can be optionally setin different temperature ranges. Usually, the relaxation velocities ofthe long-term relaxation components of the polyolefins I and II aremeasured in a temperature of from 0° C. to 150° C., preferably in such atemperature range in which the difference therebetween becomes largest.

[0156] 90° pulse width: 2.4 to 2.5 microseconds

[0157] The relaxation velocity ratio [(1/R₁)/(1/R₁)₀] can be adjusted to1.01 or higher, for example, by adopting the following methods forcontrolling the graft copolymer contained in the polyolefin-based resincomposition.

[0158] (i) Increasing the amount of the graft copolymer used;

[0159] (ii) Increasing the number of branched chains in the graftcopolymer;

[0160] (iii) Increasing the length of the branched chain in the graftcopolymer; or

[0161] (iv) Increasing both the number of branched chains and the lengthof the branched chain.

[0162] The composition of thee present invention is required to have anintrinsic viscosity [η] of 0.1 to 10 deciliter/g as measured at 135° C.in decalin. When the intrinsic viscosity [η] of the composition is lessthan 0.1 deciliter/g, the composition tends to be insufficient inmechanical properties. When the intrinsic viscosity [η] of thecomposition exceeds 10 deciliter/g, the composition tends to bedeteriorated in moldability. For these reasons, the intrinsic viscosity[η] of the composition is preferably 0.15 to 8 deciliter/g, morepreferably 0.20 to 7 deciliter/g, still more preferably 0.50 to 6deciliter/g and most preferably 0.70 to 5 deciliter/g.

[0163] Upon selecting the polyolefin I as the component (A) and thepolyolefin II as the component (B) used in the polyolefin-based resincomposition of the present invention, one of the polyolefins I and II isfirst selected to clearly determine physical properties and functions tobe improved as well as properties to be further added thereto. Then, theother polyolefin having the physical properties and functions to beimproved as well as the properties to be further added is selected.

[0164] Examples of the physical properties and functions to be improvedas well as the properties to be further added include transparency,elastic modulus, heat resistance, yield strength, breaking strength,low-temperature impact strength, heat sealing temperature, strength,tear strength, breaking elongation, crystallizability, melting point,solvent resistance, surface hardness, surface glossiness, shrinkage rateupon molding, appearance such as flow marks, mold-shape transferringproperty, etc.

[0165] The polyolefins may be selected, for example, in view of theirproperties that can be controlled by stereoregularity or by varying thecopolymerization composition or kinds of constituting monomers. Examplesof the properties of the polyolefins which can be controlled bystereoregularity are heat resistance, elastic modulus, strength,crystallizability, melting point, solvent resistance, shrinkage rateupon molding, impact strength, etc. Examples of the properties of thepolyolefins which can be controlled by varying the copolymerizationcomposition are transparency, elastic modulus, heat resistance, tensilestrength, breaking strength, low-temperature impact strength, heatsealing temperature, strength, tear strength, breaking elongation, etc.Examples of the properties of the polyolefins which can be controlled byvarying the kinds of constituting monomers include all of theabove-described properties since the properties of the polyolefins aremost remarkably influenced by the kinds of constituting monomers,thereby realizing a broad range of properties by combining the suitablemonomers.

[0166] Examples of the other thermoplastic resin as the component (D)which may be optionally blended in the polyolefin-based resincomposition of the present invention, include (1) polyolefinsexemplified above for the polyolefins I and II except for thepolyolefins used as the constituting components of the composition; (2)copolymers of olefin and a vinyl monomer, more specifically,ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer,ethylene/ethyl acrylate copolymer, ethylene/methyl methacrylatecopolymer, ionomers (metal ion-substituted products ofethylene/carboxylic acid-containing monomer copolymers such as sodiumion-neutralized products of ethylene/acrylic acid copolymer),ethylene/vinyl alcohol copolymer or the like; (3) modified olefincopolymers, more specifically, maleic anhydride-modified polypropylene,maleic anhydride-modified polyethylene or the like; (4) condensed-typepolymers, more specifically, polycarbonates, polyacetal, polyamides suchas nylon 6 and nylon 6,6, polyesters such as polyethylene terephthalateand polybutylene terephthalate, polyphenylene ethers, polysulfones,polyether sulfones, polyphenylene sulfides, thermoplastic polyimides orthe like; (5) polymers obtained by addition polymerization reaction, forexample, polymers obtained from polar vinyl monomers or diene-basedmonomers, more specifically, homopolymers such as polymethylmethacrylate, polystyrene, polyacrylonitrile, polyvinyl chloride,polybutadiene, polyisoprene and polyvinyl alcohol,acrylonitrile/butadiene/styrene copolymer, hydrogenated polymers such asSEBS, acrylonitrile/styrene copolymer, high-impact polystyrenes such asrubber-modified polystyrenes or the like; and (6) other resins such aspetroleum resins and thermoplastic elastomers. These thermoplasticresins may be used singly or in the combination of any two or morethereof.

[0167] Examples of the additive which may be optionally blended in thecomposition of the present invention include nucleating agents,antioxidants, hydrochloric acid absorbers, heat stabilizers, lightstabilizers, ultraviolet radiation absorbents, lubricants, antistaticagents, flame retardants, pigments, dyes, dispersants, copperinhibitors, neutralizers, foaming agents, plasticizers, defoamers,cross-linking agents, flow modifiers such as peroxides, weld strengthmodifiers or the like.

[0168] As the antioxidants, there may be used phenol-based, sulfur-basedand phosphorus-based antioxidants, etc. Examples of the phenol-basedantioxidants include phenols such as 2,6-di-tert-butyl-p-cresol, stearyl(3,3-dimethyl-4-hydroxybenzyl)thioglycolate,stearyl-β-(4-hydroxy-3,5-di-tert-butylphenol)propionate,distearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate,2,4,6-tris(3′,5′-di-tert-butyl-4′-hydroxybenzylthio)-1,3,5-triazine,distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl)malonate,2,2′-methylenebis(4-methyl-6-tert-butylphenol),4,4′-methylenebis(2,6-di-tert-butylphenol),2,2′-methylenebis[6-(1-methylcyclohexyl)p-cresol],bis[3,5-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester,4,4′-butylidenebis(6-tert-butyl-m-cresol),1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzylisocyanurate,1,3,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl benzene,tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,2-octylthio-4,6-di-(4-hydroxy-3,5-di-tert-butyl)phenoxy-1,3,5-triazineand 4,4′-thiobis(6-tert-butyl-m-cresol); carbonic acid oligoesters ofpolyhydric phenols such as carbonic acid oligoesters of4,4′-butylidenebis(2-tert-butyl-5-methylphenol) (e.g., polymerizationdegree: 2 to 10); or the like.

[0169] Examples of the sulfur-based antioxidants includedialkylthiodipropionates such as dilaurylthiodipropionate,dimyristylthiodipropionate and distearylthiodipropionate; esters of analkylthiopropionic acid such as butylthiopropionic acid,octylthiopropionic acid, laurylthiopropionic acid andstearylthiopropionic acid, and a polyhydric alcohol such as glycerol,trimethylol ethane, trimethylol propane, pentaerythritol andtrishydroxyethyl isocyanurate, for example, pentaerythritoltetralaurylthiopropionate; or the like.

[0170] Examples of the phosphorus-based antioxidants include trioctylphosphite, tirlauryl phosphite, tridecyl phosphite, octyl diphenylphosphite, tris(2,4-di-tert-butylphenyl)phosphite, triphenyl phosphite,tris(butoxyethyl)phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite,tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butanediphosphite, tetra-(C₁₂ to C₁₅ mixed alkyl)-4,4′-isopropylidenediphenyldiphosphite,tetra(tridecyl)-4,4′-butylidenebis(3-methyl-6-tert-butylphenol)diphosphite,tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite, tris(mono- anddi-mixed nonylphenyl)phosphite, hydrogenated-4,4′-isopropylidenediphenolpolyphosphite,bis(octylphenyl)-bis[4,4′-butylidenebis(3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4′-isopropylidenediphenol-pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,tris[4,4′-isopropylidenebis(2-tert-butylphenol)]phosphite,phenyl-diisodecyl phosphite, di(nonylphenyl) pentaerythritoldiphosphite, tris(1,3-di-stearoyloxyisopropyl)phosphite,4,4′-isopropylidenebis(2-tert-butylphenol)-di(nonylphenyl)phosphite,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphite, or thelike.

[0171] In addition, as the other antioxidants, there may also be used6-hydroxy chroman derivatives, for example, various tocopherols such asα-, β-, γ- and δ-tocopherols and mixtures thereof, 2,5-dimethyl-,2,5,8-trimethyl- and 2,5,7,8-tetramethyl-substituted products of2-(4-methyl-pent-3-enyl)-6-hydroxy chroman,2,2,7-trimethyl-5-tert-butyl-6-hydroxy chroman,2,2,5-trimethyl-7-tert-butyl-6-hydroxy chroman,2,2,5-trimethyl-6-tert-butyl-6-hydroxy chroman,2,2-dimethyl-5-tert-butyl-6-hydroxy chroman or the like.

[0172] The antioxidant may be usually used in an amount of 0.0001 to 10%by weight based on the total weight of the composition.

[0173] Examples of the hydrochloric acid absorbers include compositecompounds such as Mg₆Al₂(OH)₁₆CO₃.4H₂O, Mg₈Al₂(OH)₂₀CO₃.5H₂O,Mg₅Al₂(OH)₁₄CO₃.4H₂O, Mg₁₀Al₂(OH)₂₂(CO₃)₂.4H₂O, Mg₆Al₂(OH)₁₆HPO₄.4H₂O,Ca₆Al₂(OH)₁₆CO₃.4H₂O, Zn₆Al₂(OH)₁₆CO₃.4H₂O, Zn₆Al₂(OH)₁₆SO₄.4H₂O,Mg₆Al₂(OH)₁₆SO₄.4H₂O and Mg₆Al₂(OH)₁₂CO₃.3H₂O, calcium stearate, etc.

[0174] Examples of the ultraviolet radiation absorbents and the lightstabilizers include hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxy benzophenone,2,2′-dihydroxy-4-methoxy benzophenone and 2,4-dihydroxybenzophenone;benzotriazoles such as2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methylphenyl) benzotriazole and2-(2′-hydroxy-3′,5′-di-tert-amylphenyl) benzotriazole; benzoates such asphenyl salicylate, p-tert-butylphenyl salicylate,2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate andhexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; nickel compounds such asa nickel salt of 2,2′-thiobis(4-tert-octylphenol), a nickel salt of[2,2′-thiobis(4-tert-octylphenolato)]-n-butyl amine and a nickel salt of(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester;substituted acrylonitriles such asα-cyano-β-methyl-β-(p-methoxyphenyl)acrylic acid methyl ester; oxalicacid dianilides such as N′-2-ethylphenyl-N-ethoxy-5-tert-butylphenyloxalic acid diamide and N-2-ethylphenyl-N′-2-ethoxyphenyl oxalic aciddiamide; hindered amine compounds such as condensed products ofbis(2,2,6,6-tetramethyl-4-piperidine)sebacate,poly[((6-(1,1,3,3-tetramethylbutyl)imino)-1,3,5-triazin-2,4-diyl(4-(2,2,6,6-tetramethylpiperidyl)imino)hexamethylene] or2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol with dimethylsuccinate, or the like.

[0175] These ultraviolet radiation absorbents and light stabilizers maybe usually added in an amount of 0.0001 to 10% by weight based on thetotal weight of the composition.

[0176] Examples of the lubricants include aliphatic hydrocarbons such asparaffin waxes, polyethylene waxes and polypropylene waxes; higher fattyacids such as capric acid, lauric acid, myristic acid, palmitic acid,margaric acid, stearic acid, arachidic acid and behenic acid or metalsalts thereof such as lithium salts, calcium salts, sodium salts,magnesium salts and potassium salts; aliphatic alcohols such as palmitylalcohol, cetyl alcohol and stearyl alcohol; aliphatic amides such ascaproamide, caprylamide, caprinamide, laurylamide, myristylamide,palmitylamide and stearamide; esters of fatty acids and alcohols;fluorine compounds such as fluoroalkyl carboxylic acids or metal saltsthereof and fluoroalkyl sulfonic acid metal salts, or the like.

[0177] The nucleating agents used in the present invention may beappropriately optionally selected from conventional known nucleatingagents. The suitable nucleating agents are aromatic phosphoric acidester salts or dibenzylidene sorbitol. As the aromatic phosphoric acidester salts, there may be used, for example, compounds represented bythe general formula (X):

[0178] wherein R²⁹ is an oxygen atom, a sulfur atom or a C₁ to C₁₀divalent hydrocarbon group; R³⁰ and R³¹ are independently a hydrogenatom or a C₁ to C₁₀ hydrocarbon group in which R³⁰ and R³¹ may be thesame or different, and the two R³⁰ groups, the two R³¹ groups or R³⁰ andR³¹ may be respectively bonded to each other to from a ring; M is amono- to tri-valent metal atom; and g is an integer of 1 to 3, and

[0179] compounds represented by the general formula (XI):

[0180] wherein R³² is a hydrogen atom or a C₁ to C₁₀ hydrocarbon group;and M and g are the same as defined above.

[0181] Examples of the compounds represented by the general formula (X)include sodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate,sodium-2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate,lithium-2,2′-ethylidene -bis(4,6-di-tert-butylphenyl)phosphate,sodium-2,2′-ethylidene-bis(4-isopropyl-6-tert-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4-methyl-6-tert-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4-ethyl-6-tert-butylp henyl)phosp hate,calcium-bis[2,2′-thiobis(4-methyl-6-tert-butylphenyl)phosphate],calcium-bis[2,2′-thiobis(4-ethyl-6-tert-butylphenyl)phosphate],calcium-bis[2,2′-thiobis(4,6-di-tert-butylphenyl)phosphate],magnesium-bis[2,2′-thiobis(4,6-di-tert-butylphenyl)phosphate],magnesium-bis[2,2′-thiobis-(4-tert-octylphenyl)phosphate],sodium-2,2′-butylidene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-butylidene-bis(4,6-di-butylphenyl)phosphate,sodium-2,2′-tert-octylmethylene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-tert-octylmethylene -bis(4,6-di-tert-butylphenyl)phosphate,calcium-bis-(2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosp hate),magnesium-bis[2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate],barium-bis[2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate],sodium-2,2′-methylene-bis(4-methyl-6-tert-butylphenyl)phosphate,sodium-2,2′-methylene-bis(4-ethyl-6-tert-butylphenyl)phosphate,sodium(4,4′-dimethyl-5,6′-di-tert-butyl-2,2′-biphenyl) phosphate,calcium-bis[(4,4′-dimethyl-6,6′-di-tert-butyl-2,2′-biphenyl)phosphate],sodium-2,2′-ethylidene-bis(4-n-butyl-6-tert-butylphenyl)phosphate,sodium-2,2′-methylene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-methylene-bis(4,6-di-ethylphenyl)phosphate,potassium-2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate,calcium-bis[(2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate],magnesium-bis[(2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate],barium-bis[(2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate],aluminum-tris[2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate],aluminum-tris[2,2′-ethylidene-bis(4,6-di-tert-butylphenyl)phosphate] andcombinations thereof. Of these compounds, preferred issodium-2,2′-methylene-bis(4,6-di-tert-butylphenyl)phosphate.

[0182] Examples of the compounds represented by the general formula (XI)include sodium-bis(4-tert-butylphenyl)phosphate,sodium-bis(4-methylphenyl)phosphate, sodium-bis(4-ethylphenyl)phosphate,sodium-bis(4-isopropylphenyl)phosphate,sodium-bis(4-tert-octylphenyl)phosphate,potassium-bis(4-tert-butylphenyl)phosphate,calcium-bis(4-tert-butylphenyl)phosphate,magnesium-bis(4-tert-butylphenyl)phosphate,lithium-bis(4-tert-butylphenyl)phosphate,aluminum-bis(4-tert-butylphenyl)phosphate and combinations thereof. Ofthese compounds, preferred is sodium-bis(4-tert-butylphenyl)phosphate.

[0183] On the other hand, as the dibenzylidene sorbitol, there may beused, for example, compounds represented by the general formula (XII):

[0184] wherein R³³ is a hydrogen atom or a C₁ to C₁₀ hydrocarbon group.

[0185] Examples of the compounds represented by the general formula(XII) include 1,3,2,4-dibenzylidene sorbitol,1,3-benzylidene-2,4-p-methyl benzylidene sorbitol,1,3-benzylidene-2,4-p-ethyl benzylidene sorbitol,1,3-p-methylbenzylidene-2,4-benzylidene sorbitol,1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol,1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol,1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol,1,3,2,4-di(p-methylbenzylidene) sorbitol, 1,3,2,4-di(p-ethylbenzylidene)sorbitol, 1,3,2,4-di(p-n-propylbenzylidene) sorbitol,1,3,2,4-di(p-isopropylbenzylidene) sorbitol,1,3,2,4-di(p-n-butylbenzylidene) sorbitol,1,3,2,4-di(p-s-butylbenzylidene) sorbitol,1,3,2,4-di(p-t-butylbenzylidene) sorbitol,1,3,2,4-di(2′,4′-dimethylbenzylidene) sorbitol,1,3,2,4-di(p-methoxybenzylidene) sorbitol,1,3,2,4-di(p-ethoxybenzylidene) sorbitol,1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol,1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol,1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol,1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol,1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol,1,3,2,4-di(p-chlorobenzylidene) sorbitol and combinations thereof. Ofthese compounds, preferred are 1,3,2,4-dibenzylidene sorbitol,1,3,2,4-di(p-methylbenzylidene) sorbitol, 1,3,2,4-di(p-ethylbenzylidene)sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol,1,3,2,4-di(p-chlorobenzylidene) sorbitol and combinations thereof.

[0186] In addition, as the nucleating agents, there may also be usedmetal salts of aromatic carboxylic acids, metal salts of aliphaticcarboxylic acids or the like. Specific examples of the metal saltsinclude aluminum benzoate, aluminum p-tert-butyl benzoate, sodiumadipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate or thelike. Further, as the nucleating agents, there may also be used polymerssuch as poly-4-methyl penten-1, and inorganic compounds such as talc.

[0187] The nucleating agent may be usually added in an amount of 0.0001to 10% by weight based on the total weight of the composition.

[0188] The composition of the present invention may further containinorganic fillers. Examples of the inorganic fillers usable in thepresent invention include powered fillers, e.g., natural silicic acid orsilicates such as fine talc powder, kaolinite, calcined clay,pyrophyllite, sericite and wollastonite, carbonates such as precipitatedcalcium carbonate, heavy calcium carbonate and magnesium carbonate,hydroxides such as aluminum hydroxide and magnesium hydroxide, oxidessuch as zinc oxide, zinc white and magnesium oxide, and syntheticsilicic acid or silicates such as hydrous calcium silicate, hydrousaluminum silicate, hydrous silicic acid and anhydrous silicic acid;flake-like fillers such as mica; fibrous fillers such as basic magnesiumsulfate whiskers, calcium titanate whiskers, aluminum borate whiskers,sepiolite, PMF (processed mineral fibers), xonotlite, potassium titanateand ellestadite; balloon-shaped fillers such as glass balloons and flyash balloons, or the like.

[0189] The polyolefin-based resin composition of the present inventioncan be produced by conventionally known methods without any particularlimitation, such as the melt-kneading method using a kneader orextruder, and the method of dissolving or dispersing the constitutingcomponents in a solvent, and then removing the solvent from theresultant solution or pouring the solution into a poor solvent for thepolymer to obtain the composition.

[0190] In the melt-kneading method, the polyolefin-based resincomposition can be produced by first kneading the components using akneading apparatus such as a single-screw extruder, a twin-screwextruder, a twin-screw kneader, a Babury mixer and rolls, and thenforming the kneaded material into usually pellets.

[0191] The molded article of the present invention is formed by moldingthe thus obtained polyolefin-based resin composition by (1) method offorming the composition into a two-dimensional shape through a die, or(2) method of forming the composition into a three-dimensional shapeusing a metal mold or die. Examples of the molding method (1) includeextrusion molding, profile molding, spinning, non-woven fabric molding,multi-layer molding, etc. Examples of the molding method (2) includeinjection molding, blow molding, vacuum molding, etc.

[0192] Specific examples of the molded article of the present inventioninclude films, sheets, pipes, hollow molded products, fibers,injection-molded products, fabricated sheets, non-woven fabrics,multi-layer sheets or the like.

[0193] The present invention will be described in more detail byreference to the following examples. However, it should be noted thatthe following examples are only illustrative and not intended to limitthe invention thereto.

PRODUCTION EXAMPLE 1 Production of HDPE-g-ENB

[0194] (1) Preparation of Aluminum Oxy Compound

[0195] One thousand milliliters of a toluene solution of methylaluminoxane (1.47 mol/liter; available from Albemarle Corporation;containing 14.5% by weight of trimethyl aluminum) was distilled at 60°C. under reduced pressure (2,660 Pa) to remove the solvent therefrom,and allowed to stand under this condition for 4 hours. The resultantproduct was cooled to room temperature to obtain a dried-up methylaluminoxane.

[0196] Then, dehydrated toluene was added to the dried-up methylaluminoxane to dissolve the latter again and obtain a toluene solutionthereof having the same volume as that before the distillation. As aresult of ¹H-NMR of the resultant solution, it was confirmed that theamount of trimethyl aluminum contained in the methyl aluminoxane was3.6% by weight. Also, as a result of the measurement by fluorescentX-ray (ICP) method, it was confirmed that the total amount of aluminumcontained in the methyl aluminoxane was 1.32 mol/liter. Thereafter, theobtained solution was allowed to stand for 48 hours to precipitateinsoluble components thereof The solution separated from the precipitatewas filtered through a G5 glass filter to obtain toluene-soluble methylaluminoxane. As a result of the measurement by IPC method, it wasconfirmed that the concentration of the toluene-soluble methylaluminoxane was 1.06 mol/liter.

[0197] (2) Preparation of Carrier and Preparation of Carrier-SupportedMethyl Aluminoxane Seventy grams of SiO₂ (“P-10” available from FujiSilicia Co., Ltd.) was dried at 140° C. for 15 hours under a tracenitrogen flow. Then, 22.0 g of the thus dried SiO₂ was weighed and addedto 200 milliliter of dehydrated toluene. After the resultant mixture wascooled to a constant temperature of 0° C. while stirring, 200 milliliterof the toluene solution of methyl aluminoxane prepared in the above step(1) was dropped thereinto for 60 minutes. After completion of thedropping, the resultant solution was heated to room temperature at whichthe solution was reacted for 30 minutes, and further heated to 70° C. atwhich the solution was reacted for 3 hours. After completion of thereaction, the obtained reaction mixture was held at 60° C., and thesolid component thereof was washed with 200 milliliter of dehydratedtoluene twice and then with 200 milliliter of dehydrated heptane twice.The obtained solids were dried at 50° C. under reduced pressure toobtain 32.8 g of SiO₂-supported methyl aluminoxane. The thus obtainedSiO₂-supported methyl aluminoxane was charged again into dehydratedheptane and preserved in the form of a slurry.

[0198] (3) Preparation of Carrier-Supported Metallocene Catalyst

[0199] A 50 milliliter Schlenk tube was dried and purged with nitrogen,and then charged with 10 milliliter of dried heptane and 2 millimol (interms of aluminum atom) of the SiO₂-supported methyl aluminoxaneprepared in the above step (2), followed by stirring. One milliliter ofa toluene solution containing isopropyl cylcopentadienyl fluorenylzirconium dichloride [iPr(Cp)(Flu)ZrCl₂] in an amount of 5 micromol interms of zirconium atom, was slowly added to the SiO₂-supported methylaluminoxane, and reacted for 10 minutes.

[0200] (4) Production of Grafted Polyethylene

[0201] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 400 milliliter of dehydrated heptane and 1.0 millimol oftriusobutyl aluminum, and the mixture was stirred at room temperaturefor 10 minutes. Then, a whole amount of the supported catalyst preparedin the above step (3) was added to the autoclave.

[0202] The resultant mixture was prepolymerized at 25° C. under anethylene pressure of 0.2 MPa for 30 minutes to activate the catalyst,and then subjected to depressurization and blowing with nitrogen toremove unreacted ethylene therefrom. Then, 0.81 milliliter of a heptanesolution containing 0.5 millimol of 1,9-decadiene was added to theobtained reaction solution, and then hydrogen was introduced thereintountil reaching 0.02 MPa. After setting the reaction temperature at 60°C. and introducing ethylene until reaching an ethylene partial pressureof 0.7 MPa, the polymerization reaction was initiated and continued for210 minutes while controlling the reaction temperature to obtainpolyethylene.

[0203] After completion of the reaction, the resultant reaction solutionwas cooled to room temperature and depressurized, and after terminationof stirring, the liquid phase thereof was separated therefrom. Further,the solid reaction product was washed with a heptane solution oftriisobutyl aluminum (1.25 moliliter) three times by decantation tothereby adjust a volume of the heptane solution to 400 milliliter. Then,73 milliliter of norbornene that was subjected to activated aluminatreatment, dehydration and deoxygenation treatment, was added to theresultant solution, and the polymerization reaction was conducted at 80°C. under an ethylene pressure of 0.7 MPa for 90 minutes. Aftercompletion of the reaction, the reaction solution was depressurized torecover grafted polyethylene. As a result, it was confirmed that theamount of the thus recovered grafted polyethylene was 30.8 g.

[0204] Various properties of the thus obtained HDPE-g-ENB are shown inTable 1.

PRODUCTION EXAMPLE 2 Production of IPP-g-ENB

[0205] (1) Preparation of Carrier-Supported Catalyst Component

[0206] The same procedure as in the above step (3) of Production Example1 was repeated except that 2 micromole of racemic dimethylsilylenebis(2-methyl-4-phenyl-indenyl)zirconium[rac-SiMe₂(2-Me-4-Ph-Ind)₂ZrCl₂] was used instead of the catalyst[iPr(Cp)(Flu)ZrCl₂], to prepare a carrier-supported catalyst component.

[0207] (2) Production of Grafted PP

[0208] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 400 milliliter of dehydrated heptane and 0.5 millimol oftriisobutyl aluminum, and the mixture was stirred at room temperaturefor 10 minutes. Then, a whole amount of the supported catalyst preparedin the above step (1) was added to the autoclave.

[0209] The resultant mixture was prepolymerized at 25° C. under apropylene pressure of 0.3 MPa for 30 minutes to activate the catalyst,and then subjected to depressurization and blowing with nitrogen toremove unreacted propylene therefrom. Then, 0.81 milliliter of a heptanesolution containing 0.5 millimol of 1,9-decadiene was added to theobtained reaction solution, and then hydrogen was introduced thereintountil reaching a hydrogen pressure of 0.02 MPa. After setting thereaction temperature at 60° C. and introducing propylene until reachinga propylene partial pressure of 0.6 MPa, the polymerization reaction wasinitiated and continued for 30 minutes while controlling the reactiontemperature to obtain polypropylene.

[0210] After completion of the reaction, the resultant reaction solutionwas cooled to room temperature and depressurized, and after terminationof stirring, the liquid phase thereof was separated therefrom. Further,the obtained solid reaction product was washed with a heptane solutionof triisobutyl aluminum (1.25 mol/liter) three times by decantation tothereby adjust a volume of the heptane solution to 400 milliliter. Then,4.5 milliliter of a toluene solution containing [iPr(Cp)(Flu)ZrCl₂] inan amount of 5 micromole was dropped in the heptane solution, and theobtained solution was stirred at room temperature for 36 minutes.Further, 73 milliliter of norbornene that was subjected to activatedalumina treatment, dehydration and deoxygenation treatment, was added tothe resultant solution, and the polymerization reaction was conducted at90° C. under a ethylene pressure of 0.7 MPa for 180 minutes. Aftercompletion of the reaction, the reaction solution was depressurized torecover grafted polypropylene. As a result, it was confirmed that theyield of the thus recovered grafted polypropylene is 140 g.

[0211] Various properties of the thus obtained IPP-g-ENB are shown inTable 1.

PRODUCTION EXAMPLE 3 Production of HDPE-g-IPP

[0212] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 400 milliliter of dehydrated heptane and 0.5 millimol oftriisobutyl aluminum, and the mixture was stirred at room temperaturefor 10 minutes. Then, the same supported catalyst as prepared in theabove step (1) of Production Example 2 was added in an amount of 2micromol in terms of zirconium atom to the autoclave.

[0213] The resultant mixture was prepolymerized at 25° C. under anethylene pressure of 0.2 MPa for 30 minutes to activate the catalyst,and then subjected to depressurization and blowing with nitrogen toremove unreacted ethylene therefrom. Then, 0.81 milliliter of a heptanesolution containing 0.5 millimol of 1,9-decadiene was added to theobtained reaction solution, and further hydrogen was introducedthereinto until reaching a hydrogen pressure of 0.05 MPa. After settingthe reaction temperature at 60° C. and introducing ethylene untilreaching a ethylene partial pressure of 0.6 MPa, the polymerizationreaction was initiated and continued for 45 minutes while controllingthe reaction temperature to obtain polyethylene.

[0214] After completion of the reaction, the resultant reaction solutionwas cooled to room temperature, and depressurized and blown withnitrogen to remove unreacted ethylene. Further, the polymerizationreaction was conducted at 60° C. under a propylene pressure of 0.6 MPafor 180 minutes. After completion of the reaction, the reaction solutionwas depressurized to recover grafted polyethylene. As a result, it wasconfirmed that the yield of the thus recovered grafted polyethylene was61.1 g.

[0215] Various properties of the thus obtained HDPE-g-IPP are shown inTable 1.

PRODUCTION EXAMPLE 4 Production of IPP-g-SPP

[0216] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 400 milliliter of dehydrated toluene and 0.5 milliliter of atoluene solution containing 0.2 millimol of 1,9-decadiene. Then, methylaluminoxane (1.47 mol/liter; available from Albemarle Corporation;containing 14.5% by weight of trimethyl aluminum) was added to theautoclave such that the amount of methyl aluminoxane added was 4millimol. The resultant mixture was stirred at room temperature for 10minutes, and then 4 milliliter of a toluene solution containing[iPr(Cp)(Flu)ZrCl₂] and [rac-SiMe₂(2-Me-4-Ph-Ind)₂ZrCl₂] in amounts of 3micromol and 1 micromol, respectively, was added thereto.

[0217] The resultant mixture was graft-polymerized at 70° C. under apropylene pressure of 0.3 MPa for 10 minutes. After completion of thereaction, the obtained reaction solution was cooled to room temperatureand then depressurized to recover grafted polyethylene. As a result, itwas confirmed that the yield of the thus recovered grafted polyethylenewas 72.3 g.

[0218] Various properties of the thus obtained IPP-g-SPP are shown inTable 1.

PRODUCTION EXAMPLES 5 AND 6 Production of Propylene-based GraftCopolymer

[0219] The same procedure as in Production Example 4 was repeated exceptfor changing the production conditions as shown in Table 2, to produce apropylene-based graft copolymer.

[0220] Various properties of the thus obtained APP-g-IPP (ProductionExample 5) and SPP-g-APP (Production Example 6) are shown in Table 1.TABLE 1 Production Intrinsic Amount of p-xylene Examples and viscosityPolyene unreacted insoluble Comparative Grafted [η] content [D]polyene** content Production Examples product (dl/g) mol % N¹/N⁰ (mol %)(wt. %) Production HDPE-g-ENB 1.64 A 3.5 B 0 Example 1 ProductionIPP-g-ENB 1.71 A 3.8 B 0 Example 2 Production HDPE-g-IPP 1.41 A 2.5 B 0Example 3 Production IPP-g-SPP 1.28 A 1.8 B 0 Example 4 ProductionAPP-g-IPP 1.16 A 1.9 B 0 Example 5 Production SPP-g-APP 2.12 A 3.2 B 0Example 6 Production IPP-g-SPS 2.01 A 3.9 B 0 Example 7 ProductionHDPE-g-SPS 1.85 A 2.5 B 0 Example 8 Production IPP-g-Polyoctene 1.15 A3.5 B 0 Example 9 Production SPS-g-Polyoctene 1.50 A 3.2 B 0 Example 10Production IPP-g-LiPP 2.31 A 4.3 B 0 Example 11 Comparative — 1.50 0   —— 0 Production Example 1 Comparative EPDM-g-IPP * 0.47 * 30 about 3Production Example 2

PRODUCTION EXAMPLE 7 Production of IPP-g-SPS

[0221] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 300 milliliter of dehydrated toluene, 0.3 millimol of p-3-butenylstyrene, 100 milliliter of styrene and 1 millimol of triisobutylaluminum. Then, methyl aluminoxane (1.47 mol/liter; available fromAlbemarle Corporation; containing 14.5% by weight of trimethyl aluminum)was added to the autoclave such that the amount of methyl aluminoxaneadded was 4 millimol. The resultant mixture was stirred at roomtemperature for 10 minutes. After heating the resultant mixture to 65°C., 2 milliliter of a toluene solution containing[rac-SiMe₂(2-Me-4-Ph-Ind)₂ZrCl₂] and 6,5,6-Ti(OMe)₃ in amounts of 1micromol and 5 micromole, respectively, was added to the mixture, andthe polymerization reaction was conducted at 70° C. under a propylenepressure of 0.5 MPa for 120 minutes. After completion of the reaction,the obtained reaction solution was cooled to room temperature and thendepressurized to recover grafted polypropylene. As a result, it wasconfirmed that the yield of the thus recovered grafted polypropylene was15.6 g.

[0222] Various properties of the thus obtained IPP-g-SPS are shown inTable 1. Meanwhile, “6,5,6-Ti(OMe)₃” represents octahydrofluorenyltitanium trimethoxide.

PRODUCTION EXAMPLE 8 Production of HDPE-g-SPS

[0223] The same procedure as in Production Example 7 was repeated exceptfor using ethylene instead of propylene, to produce a graftedpolyethylene.

[0224] Various properties of the thus obtained HDPE-g-SPS are shown inTable 1.

PRODUCTION EXAMPLE 9 Production of IPP-g-Polyoctene

[0225] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 400 milliliter of dehydrated heptane and 0.5 millimol oftriusobutyl aluminum, and the resultant mixture was stirred at roomtemperature for 10 minutes. Then, the same catalyst as prepared in theabove step (1) of Production Example 2 was entirely added in an amountof 2 micromole in terms of zirconium atom to the autoclave.

[0226] The resultant mixture was prepolymerized at 25° C. under apropylene pressure of 0.3 MPa for 30 minutes to activate the catalyst,and then subjected to depressurization and blowing with nitrogen toremove unreacted propylene therefrom. Then, 0.49 milliliter of a heptanesolution containing 0.3 millimol of 1,9-decadiene was added to theobtained reaction solution, and further hydrogen was introducedthereinto until reaching a hydrogen pressure of 0.02 MPa. After settingthe reaction temperature at 60° C. and introducing propylene untilreaching a propylene partial pressure of 0.6 MPa, the polymerizationreaction was initiated and continued for 30 minutes while controllingthe reaction temperature to obtain polypropylene.

[0227] After completion of the reaction, the resultant reaction solutionwas cooled to room temperature and depressurized, and after terminationof the stirring, the liquid phase was separated therefrom. Further, thesolid reaction product was washed with a heptane solution of triisobutylaluminum (1.25 mol/liter) three times by decantation to thereby adjust avolume of the heptane solution to 100 milliliter.

[0228] To the obtained solution was dropped 4.5 milliliter of a toluenesolution containing a double cross-linked complex(Me₂Si)₂[3-CH₂SiMe₃-Ind]₂ZrCl₂ in an amount of 3 micromol, followed bystirring the solution at room temperature for 5 minutes. Further, 150 gof 1-octene was added to the resultant solution, and polymerized at 60°C. for 60 minutes. After completion of the reaction, the reactionsolution was depressurized to recover grafted polypropylene. As aresult, it was confirmed that the yield of the thus recovered graftedpolypropylene was 76 g.

[0229] Various properties of the thus obtained IPP-g-polyoctene areshown in Table 1.

PRODUCTION EXAMPLE 10 Production of SPS-g-Polyoctene

[0230] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 300 milliliter of dehydrated toluene, 0.3 millimol of p-3-butenylstyrene, 150 g of 1-octene, 100 milliliter of styrene and 1 millimol oftriisobutyl aluminum. Then, methyl aluminoxane (1.47 mol/liter;available from Albemarle Corporation; containing 14.5% by weight oftrimethyl aluminum) was added to the autoclave such that the amount ofmethyl aluminoxane added was 4 millimol. The resultant mixture wasstirred at room temperature for 10 minutes. After heating the resultantmixture to 60° C., 2 milliliter of a toluene solution containing adouble cross-linked complex (Me₂Si)₂[3-CH₂SiMe₃-Ind]₂ZrCl₂ and6,5,6-Ti(OMe)₃ in amounts of 3 micromol and 5 micromol, respectively,was added to the above reaction mixture, and the polymerization reactionwas conducted at 60° C. for 120 minutes. After completion of thereaction, the obtained reaction solution was cooled to room temperatureand then depressurized to recover grafted polystyrene. As a result, itwas confirmed that the yield of the thus recovered grafted polystyrenewas 42 g.

[0231] Various properties of the thus obtained SPS-g-polyoctene areshown in Table 1.

PRODUCTION EXAMPLE 11 Production of IPP-g-Low-Stereoregular IsotacticPolypropylene

[0232] A 1.6 liter stainless steel pressure-tight autoclave was chargedwith 400 milliliter of dehydrated heptane, 0.3 millimol of 1,9-decadieneand 0.5 millimol of triisobutyl aluminum, and the resultant mixture wasstirred at room temperature for 10 minutes. Then, methyl aluminoxane(1.47 mol/liter; available from Albemarle Corporation; containing 14.5%by weight of trimethyl aluminum) was added to the autoclave such thatthe amount of methyl aluminoxane added was 2 millimol, and further 2milliliter of a toluene solution containing as a metallocene catalyst,(Me₂Si)₂[3-CH₂SiMe₃-Ind]₂ZrCl₂ and [rac-SiMe₂(2-Me-4-Ph-Ind)₂ZrCl₂] inamounts of 0.5 micromol and 1 micromol, respectively, was added to theabove reaction mixture. After setting the reaction temperature at 50° C.and introducing propylene until reaching a propylene partial pressure of0.7 MPa, the polymerization reaction was initiated and continued for 30minutes while controlling the reaction temperature to obtainpolypropylene.

[0233] After elapse of the reaction time, while maintaining the reactiontemperature, the reaction solution was depressurized and blown withnitrogen to completely remove gaseous components such as unreactedpropylene therefrom. After completion of the polymerization reaction,the obtained reaction solution was depressurized to recoverpolypropylene. As a result, it was confirmed that the yield of the thusrecovered polypropylene was 62 g.

[0234] Various properties of the thus obtained IPP-g-low-stereoregularisotactic polypropylene are shown in Table 1.

COMPARATIVE PRODUCTION EXAMPLE 1 Production of Mixture of HDPE and ENB

[0235] The same procedure as in Production Example 1 was repeated exceptfor using no 1,9-decadiene in the step (4) of Production Example 1,thereby producing a mixture of polyethylene and ethylene/norbornenecopolymer (ENB). As a result, it was confirmed that 28.5 g of themixture was produced.

[0236] Various properties of the thus obtained mixture are shown inTable 1.

COMPARATIVE PRODUCTION EXAMPLE 2 Production of EPDM-g-IPP

[0237] EPDM-g-IPP was produced according to the method described inExample 1 of Japanese Patent Application Laid-open No. Hei3-28209.Various properties of the thus obtained EPDM-g-IPP are shown in Table 1.

[0238] Meanwhile, in Table 1, “Amount of unreacted polyene” represents acontent of unreacted unsaturated groups in polyene present in thepolymers to be copolymerized. TABLE 2 Catalytic component PropyleneProduction Amount used pressure Temp. Time Yield Examples Compound(μmol) (MPa) (° C.) (min) (g) Production (Me₂Si)Cp*(t-BuN)TiCl₂ 4 0.3 7030 96.7 Example 5 rac-Me₂Si[2-Me-4-Ph-Ind] 0.5 ₂ZrCl₂ Production(Me₂Si)Cp*(t-BuN)TiCl₂ 4 0.7 50 30 55.7 Example 6 iPr(Cp)(Flu)ZrCl₂ 3

EXAMPLES 1 TO 10 AND COMPARATIVE EXAMPLES 1 TO 7

[0239] (1) Preparation of Composition

[0240] The resin components shown in Table 3 were mixed and dissolved in300 milliliter of p-xylene using 500 ppm of BHT as an antioxidant (basedon the total amount of the resin components) under the conditions shownin Table 3. It was confirmed that the amount of the polymers dissolvedwas 3 to 3.3 g. After 3 hours, it was recognized that the resincomponents were uniformly dissolved. Then, the polymer mixed solutionwas charged into 3 liters of methanol while stirring to re-precipitateand recover solids. After filtering, the obtained solids were dried at80° C. under reduced pressure until reaching a constant weight, therebyobtaining the polyolefin composition.

[0241] (2) Solid ¹H-NMR Measurement

[0242] The resin composition produced in the above step (1) was formedinto a plate shape using a heat press, and pulverized into pellets as aspecimen. The specimen was subjected to solid ¹H-NMR by theabove-mentioned method. The results are shown in Table 3.

[0243] The measurements of the respective compositions were performed atthe following temperatures: Measuring Examples and ComparativeComposition temperature (° C.) Examples HDPE/ENB 100 Example 1; Example2; Comparative Example 1; Comparative Example 2 IPP/ENB 130 Example 3;Example 4; Comparative Example 3 IPP/SPP 120 Example 5; ComparativeExample 4 IPP/APP 30 Example 6; Example 7; Comparative Example 5 IPP/SPS90 Example 8; Example 9; Comparative Example 6 IPP/HDPE 90 Example 10;Comparative Example 7

[0244] Evaluation of Uniform Dissolvability

[0245] The uniform dissolvability was evaluated according to the abovemethod of measuring the p-xylene insoluble content at 140° C. In thecase where no insoluble components remained in the 150 mesh container,the dissolvability was regarded as “Good”. TABLE 3-1 Com. Com. Com. Ex.1 Ex. 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 3 Composition of resins HDPE^((A))(wt. %) 83 83 83 83 — — — ENB^((B)) (wt. %) 17 17 17 17 17 17 17IPP^((C)) (wt. %) — — — — 83 83 83 SPP^((D)) (wt. %) — — — — — — —APP^((E)) (wt. %) — — — — — — — SPS^((F)) (wt. %) — — — — — — — Graftcopolymer Pro. Pro. — Comp. Pro. Pro. — (wt. part) Ex. Ex. 1 Pro. Ex. 2Ex. 2 1* (10) Ex. (5) (10) (5) 1** (5) Relaxation velocity 1.14 1.20 — —2.31 2.40 — (1/R₁) (1/sec) Relaxation velocity — — 1.08 1.08 — — 2.15(1/R₁)₀ (1/sec) Relaxation 1.06 1.11 — 1.00 1.07 1.12 — velocity ratio[(1/R₁)/(1/R₁)₀] Uniform Good Good Good Good Good Good Gooddissolvability Intrinsic viscosity of 1.89 1.90 1.86 1.92 2.50 2.45 2.40resin composition [η] (dl/g)

[0246] TABLE 3-2 Com. Com. Com. Ex. 5 Ex. 4 Ex. 6 Ex. 7 Ex. 5 Ex. 8 Ex.9 Ex. 6 Composition of resins HDPE^((A)) — — — — — — — — (wt. %)ENB^((B)) (wt. %) — — — — — — — — IPP^((C)) (wt. %) 83 83 83 83 83 83 8383 SPP^((D)) (wt. %) 17 17 — — — — — — APP^((E)) (wt. %) — 17 17 17 — —— SPS^((F)) (wt. %) — — — — 17 17 17 Graft Pro. — Pro. Pro. — Pro. Pro.— copolymer Ex. 4 Ex. 5 Ex. 5 Ex. 7 Ex. 7 (wt. part) (10) (5) (10) (5)(10) Relaxation 2.30 — 1.38 1.37 — 0.426 0.435 — velocity (1/R₁) (1/sec)Relaxation — 2.19 — — 1.30 — — 0.405 velocity (1/R₁)₀ (1/sec) Relaxation1.05 — 1.06 1.05 — 1.05 1.07 — velocity ratio [(1/R₁)/(1/R₁)₀] UniformGood Good Good Good Good Good Good Good dissolvability Intrinsic 2.462.40 2.82 2.90 2.80 2.81 2.75 2.70 viscosity of resin composi- tion [η](dli/g)

[0247] TABLE 3-3 Comparative Example 10 Example 7 Composition of resins20   20   HDPE^((A)) (wt. %) — — ENB^((B)) (wt. %) 80   80   IPP^((C))(wt. %) — — SPP^((D)) (wt. %) — — APP^((E)) (wt. %) — — SPS^((F)) (wt.%) — — Graft copolymer (wt. part) Production — Example 3 (5) Relaxationvelocity (1/R₁) (1/sec)  1.17 Relaxation velocity (1/R₁)₀ (1/sec) — 1.08 Relaxation velocity ratio [(1/R₁)/(1/R₁)0]  1.08 — Uniformdissolvability Good Good Intrinsic viscosity of resin composition  2.29 2.20 [η] (dl/g)

[0248] In Comparative Examples 1, 5 and 6 in which the graft copolymerwas not blended in the resin composition, no compatilizing component waspresent in the system when the polyolefins I and II were melt-kneaded toproduce the resin composition. For this reason, interfacial adhesionbetween the polyolefins I and II was not enhanced, thereby failing tocontrol the particle size of dispersed particles (particles of thepolyolefin I or II) in the composition. Therefore, it was not possibleto prepare a composite material composed of a polyolefin-based resinwhich had properties as required.

[0249] In Comparative Example 2, although the graft copolymer wasblended in the polyolefin-based resin composition, the relaxationvelocity ratio of the obtained composition was 1.00. Therefore, it wasconfirmed that the miscibility between the polyolefins I and II was notsufficiently enhanced. As a result, it was not possible to prepare acomposite material composed of a polyolefin-based resin which hadproperties as required.

[0250] Meanwhile, although a resin composition containing the graftcopolymer obtained in Comparative Production Example 2 was notillustrated herein, it is expected that since the graft copolymerobtained in Comparative Production Example 2 contains a large amount ofresidual carbon-to-carbon double bonds derived from the polyene unit andalso has a large p-xylene insoluble content, the resin composition inwhich the graft copolymer of Comparative Production Example 2 isblended, tends to suffer from poor heat resistance and formation ofblobs.

[0251] In contrast with the above Comparative Examples, in Examples ofthe present invention, the polyolefin-based resin compositions havingspecific properties were produced using the specific graft copolymers.For this reason, the miscibility between the polyolefins I and II aswell as the interfacial adhesion therebetween can be sufficientlyenhanced, and the particle size of dispersed particles can also be wellcontrolled. As a result, the obtained resin compositions can be improvedand well-controlled in properties such as mechanical strength, heatresistance, low-temperature impact strength and solvent resistance.

[0252] Further, the graft copolymers used in the respective Examples ofthe present invention have substantially no p-xylene insolublecomponents, and contains substantially no residual carbon-to-carbondouble bonds. Therefore, the resin compositions of the respectiveExamples of the present invention which were produced using the graftcopolymers, are free from blobs causing concentrated stress and canexhibit improved mechanical strength and excellent thermal stability.

INDUSTRIAL APPLICABILITY

[0253] According to the present invention, it is possible to obtain apolyolefin-based resin composition that can be readily controlled inproperty-determining factors such as morphology and interfacial strengthby combination of optional polyolefin-based resins, in particular,combination of non-compatible resins, and can provide a compositematerial composed of polyolefin-based resins which has excellentproperties as required.

What is claimed is:
 1. A polyolefin-based resin composition, comprisingas essential components: (A) a polyolefin I produced from at least onemonomer selected from the group consisting of C₂ to C₂₀ α-olefins,cyclic olefins and aromatic vinyl compounds; (B) a polyolefin IIproduced from at least one monomer selected from the group consisting ofC₂ to C₂₀ α-olefins, cyclic olefins and aromatic vinyl compounds, whichdiffers in at least one of kinds of constituting monomer units,stereoregularity, copolymerization composition, copolymerization typeand kinds of different bonds, from said polyolefin I; and (C) a graftcopolymer produced by bonding said polyolefins I and II to each otherthrough a polyene, which has a xylene-insoluble content at 140° C. of 0to 2.5% by weight, and a polyene-derived residual carbon-to-carbondouble bond content of 0 to 0.15 mol %, wherein (a) a ratio[1/R₁)/(1/R₁)₀] of a relaxation velocity (1/R₁) of a long-termrelaxation component measured by a solid ¹H-NMR method about thecomposition to a relaxation velocity (1/R₁)₀ of a long-term relaxationcomponent measured by a solid ¹H-NMR method about a resin mixture ofonly the components (A) and (B) is 1.01 or higher; and (b) an intrinsicviscosity [η] of the composition is in the range of 0.1 to 10deciliter/g as measured in decalin at 135° C.
 2. The polyolefin-basedresin composition according to claim 1, wherein said component (A) andsaid component (B) are contained at a weight ratio of 1:99 to 99:1, andfurther said component (C) is contained in an amount of 0.01 to 30% byweight based on the total weight of said components (A) and (B).
 3. Thepolyolefin-based resin composition according to claim 1 or 2, whereinsaid polyolefin I as component (A) contains ethylene units in an amountof more than 50 mol %.
 4. The polyolefin-based resin compositionaccording to claim 1 or 2, wherein said polyolefin I as component (A)contains propylene units in an amount of more than 50 mol %.
 5. Thepolyolefin-based resin composition according to claim 1 or 2, whereinsaid polyolefin I as component (A) contains cyclic olefin units in anamount of more than 50 mol %.
 6. The polyolefin-based resin compositionaccording to claim 1 or 2, wherein said polyolefin I as component (A)contains aromatic vinyl compound units in an amount of more than 50 mol%.
 7. The polyolefin-based resin composition according to any of claims1 to 6, further comprising (D) the other thermoplastic resin.
 8. Thepolyolefin-based resin composition according to any of claims 1 to 7,further comprising an additive.
 9. A molded article produced from thepolyolefin-based resin composition as claimed in any of claims 1 to 8.